Amphipathic compound having succinic acid skeleton

ABSTRACT

An amphipathic compound represented by any of the following Formulas: ##STR1## (R 1  is a linear or branched, saturated hydrocarbon group having 6 to 48 carbon atoms, or a linear or branched, unsaturated hydrocarbon group containing 1 to 12 unsaturated double bond and having 6 to 48 carbon atoms; Y is NH, N--(CH 2  --CH═CH 2 ), or O; Q is --CH 2  --C(R 2 )═CH 2  or --R 4  --O--CO--C(R 2 )═CH 2  ; and M is alkali metal, an ammonium group, or --(CH 2  CH 2  O) m  H), a copolymer of the amphipatic compound with a copolymerizable ethylenically unsaturated compound and, a paper making additive containing a water soluble or dispersible high molecular compound as an active ingredient and processes for producing these high molecular compounds.

This application is a divisional, of application Ser. No. 08/658,254,filed Jun. 4, 1996, U.S. Pat. No. 5,872,287.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

The present invention relates to an amphipathic compound, a highmolecular compound using the same, and a process for producing the same.

Since the amphipathic compound of the present invention has at least onedouble bond in a molecule and is capable of polymerizing with variousethylenically unsaturated compounds, it is a useful compound as a rawmaterial for a synthetic resin. Further, the amphipathic compound of thepresent invention is a compound which is classified as a reactivesurfactant, and a high molecular compound obtained by copolymerizing theamphipathic compound of the present invention with an ethylenicallyunsaturated compound is used for plasticizers, heat resistant resins,lubricants, antistatic agents, paints, adhesives, dispersants, andadditives for cement. A copolymer of the amphipathic compound of thepresent invention with a hydrophilic ethylenically unsaturated compoundis soluble or dispersible in water and useful as a high molecular typesurfactant. In particular, the copolymer with (meth)acrylamide has ahigh utility value as a novel paper making additive, which can improvesizing performance and paper reinforcing performance at the same time.

(2) Description of the Related Art Japanese Patent Laid-open SHO63-235595 and HEI 5-125681 disclose alkenyl succinic acid semi-ester anda reaction product of alkyl or alkenyl succinic acid with an alkyleneoxide adduct of polyhydric alcohol. However, the amphipathic compound ofthe present invention is a novel compound which has not so far beenreported. Further, the copolymer of the amphipathic compound of thepresent invention with an ethylenically unsaturated compound is also anovel compound which has not so far been reported.

SUMMARY OF THE INVENTION

An object of the present invention is to provide (1) a novel amphipathiccompound having a succinic acid derivative skeleton with a polymerizableunsaturated bond, (2) a novel amphipathic compound having phthalic acidand its derivative skeletons, (3) a high molecular compound obtained bycopolymerizing the amphipathic compound having a succinic acidderivative skeleton with a copolymerizable ethylenically unsaturatedcompound, (4) a high molecular compound obtained by copolymerizing theamphipathic compound having phthalic acid and its derivative skeletonswith a copolymerizable ethylenically unsaturated compound, (5) a watersoluble or dispersible high molecular compound obtained bycopolymerizing the amphipathic compound having a succinic acidderivative skeleton with a hydrophilic ethylenically unsaturatedcompound, (6) a water soluble or dispersible high molecular compoundobtained by copolymerizing the amphipathic compound having phthalic acidand its derivative skeletons with the copolymerizable, hydrophilicethylenically unsaturated compound, and a paper making additivecontaining the water soluble or dispersible high molecular compounds of(5) and (6) as an active ingredient. Among them, particularly thecopolymer with (meth)acrylamide is abbreviated as a PAM group sizingagent.

Further, an another object of the present invention is to provide (7) anemulsion having an ability to form a polymer film having excellent heatresistance and water resistance, in which the amphipathic compound ofthe present invention is used as an emulsifier, (8) a process forproducing an amphipathic high molecular compound having a high molecularweight and a low viscosity by copolymerizing the amphipathic compound ofthe present invention with a hydrophilic ethylenically unsaturatedcompound in the presence of a colloidizing agent, and (9) a process forproducing an emulsion having a heteromorphic structure, obtained bypolymerizing a hydrophobic ethylenically unsaturated compound in thepresence of the amphipathic compound of the present invention.

That is, the present invention relates to:

1) an amphipathic compound having a succinic acid skeleton representedby any of the following Formulas (1) to (4): ##STR2## wherein R₁ is alinear or branched saturated hydrocarbon group having 6 to 48 carbonatoms, or a linear or branched unsaturated hydrocarbon group containing1 to 12 unsaturated double bonds and having 6 to 48 carbon atoms; R₂ andR₃ are independently a hydrogen atom or a methyl group; R₄ is a linearor branched saturated hydrocarbon group having 2 to 6 carbon atoms; M isa hydrogen atom, an alkali metal, or an ammonium group; and X is NH orN--(CH₂ --CH═CH₂);

2) an amphipathic compound having a succinic acid skeleton representedby any of the following Formulas (5) to (8): ##STR3## wherein R₁ is alinear or branched saturated hydrocarbon group having 6 to 48 carbonatoms, or a linear or branched unsaturated hydrocarbon group containing1 to 12 unsaturated double bonds and having 6 to 48 carbon atoms; R₂ andR₃ are independently a hydrogen atom or a methyl group; R₄ is a linearor branched saturated hydrocarbon group having 2 to 6 carbon atoms; Y isNH, N--(CH₂ --CH═CH₂), or O; and m is an integer of 1 to 100;

3) an amphipathic compound in which R₁ in Formulas (1) to (4) of 1) isrepresented by any of the following Formulas (9) to (13): ##STR4##wherein R₅ and R₆ are independently a hydrogen atom, or a linear alkylgroup or alkenyl group of C₁ to C₂₃, provided that a carbon number of(R₅ +R₆) falls in a range of 3 to 45; ##STR5## wherein p is an integerof 0 to 6; 4) an amphipathic compound in which R₁ in Formulas (5) to (8)of 2) is represented by any of the following Formulas (9) to (13):##STR6## wherein R₅ and R₆ are independently a hydrogen atom, or alinear alkyl group or alkenyl group of C₁ to C₂₃, provided that a carbonnumber of (R₅ +R₆) falls in a range of 3 to 45; ##STR7## wherein p is aninteger of 0 to 6; 5) an amphipathic compound having any of phthalicacid or tetrahydrophthalic acid, hexahydrophthalic acid,norbornenedicarboxylic acid, and norbornanedicarboxylic acid structuresrepresented by following Formulas (14) to (17): ##STR8## wherein R₇ andR₈ are independently a hydrogen atom or a methyl group; R₉ is a linearor branched saturated hydrocarbon group having 2 to 6 carbon atoms; R₁₀and R₁₁ are independently a hydrogen atom or a methyl group; M is ahydrogen atom, an alkali metal, or an ammonium group; and X is NH orN--(CH₂ --CH═CH₂);

6) a high molecular compound obtained by copolymerizing 0.1 to 90.0weight % of an amphipathic compound having a succinic acid skeletonrepresented by any of Formulas (18) to (21) or a mixture thereof with10.0 to 99.9 weight % of a copolymerizable ethylenically unsaturatedcompound: ##STR9## wherein R₁ is a linear or branched saturatedhydrocarbon group having 6 to 48 carbon atoms, or a linear or branchedunsaturated hydrocarbon group containing 1 to 12 unsaturated doublebonds and having 6 to 48 carbon atoms; R₂ and R₃ are independently ahydrogen atom or a methyl group; R₄ is a linear or branched saturatedhydrocarbon group having 2 to 6 carbon atoms; M is a hydrogen atom, analkali metal, or an ammonium group; and Y is NH, N--(CH₂ --CH═CH₂), orO;

7) a water soluble or dispersible amphipathic high molecular compoundobtained by copolymerizing 0.1 to 90.0 weight % of the compoundrepresented by any of Formulas (18) to (21) as described in 6) or amixture thereof with 10.0 to 99.9 weight % of a hydrophilicethylenically unsaturated compound;

8) a paper making additive containing the water soluble or dispersibleamphipathic high molecular compound as described in 7) as an activeingredient;

9) a high molecular compound obtained by copolymerizing 0.1 to 90.0weight % of the compound represented by any of Formulas (5) to (8) asdescribed in 2) or a mixture thereof with 10.0 to 99.9 weight % of acopolymerizable ethylenically unsaturated compound;

10) a water soluble or dispersible amphipathic high molecular compoundobtained by copolymerizing 0.1 to 90.0 weight % of the compoundrepresented by any of Formulas (5) to (8) as described in 2) or amixture thereof with 10.0 to 99.9 weight % of a hydrophilicethylenically unsaturated compound;

11) a paper making additive containing the water soluble or dispersibleamphipathic high molecular compound as described in 10) as an activeingredient;

12) a high molecular compound having phthalic acid or tetrahydrophthalicacid, hexahydrophthalic acid, norbornenedicarboxylic acid, andnorbornanedicarboxylic acid structures on side chains which is obtainedby copolymerizing 0.1 to 90.0 weight % of a compound represented by anyof Formulas (22) to (25) or a mixture thereof with 10.0 to 99.9 weight %of a copolymerizable ethylenically unsaturated compound: ##STR10##wherein R₇ and R₈ are independently a hydrogen atom or a methyl group;R₉ is a linear or branched saturated hydrocarbon group having 2 to 6carbon atoms; R₁₀ and R₁₁ are independently a hydrogen atom or a methylgroup; M is a hydrogen atom, an alkali metal, or an ammonium group; andY is NH, N--(CH₂ --CH═CH₂), or O;

13) a water soluble or dispersible amphipathic high molecular compoundobtained by copolymerizing 0.1 to 90.0 weight % of the compoundrepresented by Formulas (22) to (25) as described in 12) or a mixturethereof with 10.Q to 99.9 weight % of a hydrophilic ethylenicallyunsaturated compound;

14) a paper making additive containing the water soluble or dispersibleamphipathic high molecular compound as described in 13) as an activeingredient;

15) a reactive surfactant represented by any of Formulas (5) to (8), anyof Formulas (18) to (21), or any of Formulas (22) to (25): ##STR11##wherein R₁ is a linear or branched saturated hydrocarbon group having 6to 48 carbon atoms, or a linear or branched unsaturated hydrocarbongroup containing 1 to 12 unsaturated double bonds and having 6 to 48carbon atoms; R₂ and R₃ are independently a hydrogen atom or a methylgroup; R₄ is a linear or branched saturated hydrocarbon group having 2to 6 carbon atoms; Y is NH, N--(CH₂ --CH═CH₂), or O; and m is an integerof 1 to 100; ##STR12## wherein R₁ is a linear or branched saturatedhydrocarbon group having 6 to 48 carbon atoms, or a linear or branchedunsaturated hydrocarbon group containing 1 to 12 unsaturated doublebonds and having 6 to 48 carbon atoms; R₂ and R₃ are independently ahydrogen atom or a methyl group; R₄ is a linear or branched saturatedhydrocarbon group having 2 to 6 carbon atoms; M is a hydrogen atom, analkali metal, or an ammonium group; and Y is NH, N--(CH₂ --CH═CH₂), orO; ##STR13## wherein R₇ and R₈ are independently a hydrogen atom or amethyl group; R₉ is a linear or branched saturated hydrocarbon grouphaving 2 to 6 carbon atoms; R₁₀ and R₁₁ are independently a hydrogenatom or a methyl group; M is a hydrogen atom, an alkali metal, or anammonium group; and Y is NH, N--(CH₂ --CH═CH₂) or O;

16) a water-dispersing type resin composition obtained byemulsion-polymerizing 0.1 to 20 weight % of the reactive surfactant asdescribed in 15) with 80 to 99.9 weight % of an ethylenicallyunsaturated compound;

17) a high molecular surfactant obtained by copolymerizing 0.1 to 50weight % of the reactive surfactant as described in 15) with 50 to 99.9weight % of a hydrophilic ethylenically unsaturated compound;

18) a water-dispersing type resin composition obtained byemulsion-polymerizing an ethylenically unsaturated compound in thepresence of the high molecular surfactant as described in 17);

19) a process for producing an amphipathic high molecular compound,characterized in that the reactive surfactant as described in 15) iscopolymerized with a hydrophilic, nonionic unsaturated compound in anaqueous medium in the presence of a colloidizing agent;

20) a process for producing an amphipathic high molecular compound asdescribed in 19), wherein the reactive surfactant of 0.1 to 90 weight %as described in 15) is copolymerized with the hydrophilic, nonionicethylenically unsaturated compound of 10 to 99.9 weight % in the aqueousmedium in the presence of the colloidizing agent of 0.1 to 10 moles permole of the reactive surfactant;

21) a process for producing an amphipathic high molecular compound asdescribed in 19) or 20), wherein the colloidizing agent comprises acombination of at least one selected from inorganic acid, organic acid,inorganic base, and organic base;

22) a process for producing an amphipathic high molecular compound asdescribed in 19), wherein the reactive surf actant has at least onecarboxyl group in the molecule;

23) a process for producing an amphipathic high molecular compound asdescribed in 22), wherein the 10 to 99.9 weight % of hydrophilic,nonionic ethylenically unsaturated compound is copolymerized with 0.1 to90 weight % of the reactive surfactant having at least one carboxylgroup in the molecule in the aqueous medium in the presence of thecolloidizing agent of 0.1 to 10 moles per mole of the reactivesurfactant;

24) a process for producing an amphipathic high molecular compound asdescribed in 23), wherein the colloidizing agent comprises a combinationof at least one selected from inorganic acid, organic acid, inorganicbase, and organic base; and

25) a water dispersible type resin composition obtained byemulsion-polymerizing an ethylenically unsaturated compound in thepresence of the amphipathic high molecular compound as described in 17).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an Infrared rays (IR) absorption spectrum of the compoundobtained in Example 1.

FIGS. 2a and 2b are ¹ H-NMR spectrum of the compound obtained in Example1.

FIGS. 3a and 3b are ¹³ C-NMR spectrum of the compound obtained inExample 1.

FIG. 4 is an IR absorption spectrum of the compound obtained in Example2.

FIGS. 5a and 5b are ¹ H-NMR spectrum of the compound obtained in Example2.

FIGS. 6a and 6b are ¹³ C-NMR spectrum of the compound obtained inExample 2.

FIG. 7 is an IR absorption spectrum of the compound obtained inReference Example 1.

FIG. 8 is a ¹ H-NMR spectrum of the compound obtained in ReferenceExample 1.

FIG. 9 is a ¹³ C-NMR spectrum of the compound obtained in ReferenceExample 1.

FIG. 10 is an IR absorption spectrum of the compound obtained in Example14.

FIG. 11 is a ¹ H-NMR spectrum of the compound obtained in Example 14.

FIG. 12 is a ¹³ C-NMR spectrum of the compound obtained in Example 14.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The amphipathic compound used in the present invention is classifiedinto (1) to (4); that is, (1) an allyl compound having a succinamidestructure substituted with a hydrophobic group in the skeleton; (2) anallyl or vinyl compound having a succinic acid ester structuresubstituted with a hydrophobic group in the skeleton; (3) an ethoxylatecompound obtained by reacting an allyl or vinyl compound having asuccinamide or succinic acid ester structure substituted with ahydrophobic group in the skeleton with ethylene oxide (hereinafterabbreviated as EO); and (4) an allyl compound having an amide or esterstructure of phthalic acid and derivative thereof, or a mixture of atleast two compounds selected from them. Among them, the compound groupsexcluding the allyl compound having a succinic acid ester structuredescribed in (2) and the compound having an ester structure of aphthalic acid derivative described in (4) are the novel compounds of thepresent invention. The derivatives of phthalic acid as described in thepresent specification include tetrahydrophthalic acid derivatives,hexahydrophthalic acid, and dicarboxylic acid derivatives havingnorbornene and norbornane structures (endomethylenetetrahydrophthalicacid and endomethylenehexahydrophthalic acid, respectively).

(1) The allyl compound having a succinamide structure substituted with ahydrophobic group in the skeleton is produced by the reaction of acompound (hereinafter abbreviated as ASA) obtained by reacting betweenoligomers of olefins produced from ethylene, propylene, isobutene andbutadiene and maleic anhydride, with allylamine (MA), diallylamine (DA)or methallylamine (hereinafter, the reaction products with ASA shall beabbreviated as ASA-MA and ASA-DA).

The examples of ASA are compounds obtained by known techniques, such as1 addition products of maleic anhydride to linear or branched α-olefinshaving 6 to 48 carbon atoms including 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-docosene,or a mixture thereof, 2 reaction products of internal olefins obtainedby isomerizing linear or branched α-olefins having 6 to 48 carbon atomsor a mixture thereof in the presence of a catalyst with maleicanhydride, and 3 reaction products of internal olefins obtained bysubjecting linear or branched α-paraffins having 6 to 48 carbon atoms ora mixture thereof to dehydrogenation with maleic anhydride. They may bea mixture of the compounds having a different number of carbon atoms orhaving double bonds in different positions in internal olefins. Further,there may be used saturated hydrocarbons obtained by hydrogenatingolefins after the reaction with maleic anhydride. Hereinafterabbreviated are a reaction product of an oligomer of ethylene withmaleic anhydride as ESA, a reaction product of an oligomer of propylenewith maleic anhydride as PSA, and a reaction product of an oligomer ofisobutene with maleic anhydride as BSA. In general, a raw material forESA is an oligomer produced by a process in which ethylene is subjectedto oligomerization at high temperatures and high pressure with a Zieglercatalyst such as triethylaluminum, or an isomer thereof. Raw materialsfor PSA and BSA are oligomers obtained by polymerizing propylene orisobutene in the presence of an acid catalyst such as solid phosphoricacid and liquid phosphoric acid or a Friedel-Crafts catalyst such asaluminum chloride, or isomers thereof. The polymers are obtained in theform of olefin mixtures having distributions in the carbon numbers.Oligomers obtained by fractional distillation under atmospheric pressureor a reduced pressure are used if necessary, and those having 6 to 48carbon atoms are suitable. If the carbon number of the oligomers is lessthan 6 or exceeds 48, the amphipathic character as a reactive surfactantsuch as ASA-MA and ASA-DA is interfered, and therefore such oligomers donot meet the objects of the present invention.

The reaction of ASA with allylamine, diallylamine and methallylamine isusually carried out by adding dropwise allylamine or diallylamine to anorganic solvent solution of ASA while stirring. The organic solventsusable as a reaction solvent may be any ones as long as they dissolveboth ASA and allylamines, and the examples thereof include acetone,2-butanone, benzene, toluene, xylene, pentane, hexane, cyclohexane, DMF,DMSO, THF, diethyl ether, dioxane, dichloromethane, dichloroethane, andchloroform. Alcohol solvents such as methanol, ethanol, isopropanol,methyl cellosolve, ethyl cellosolve, 2-ethylhexanol and cyclohexanolcause partial esterification with succinic anhydride in some cases.However, since succinic anhydride is highly reactive with allylamines,and in general, ester is formed only in a small amount, alcohol solventscan be employed as well as for uses in which mixing of esters does notexert great influences on the physical properties of the resins. ASAwhich is liquid at room temperatures, such as ASA having a small numberof carbon atoms and ASA using an internal olefin as a raw material canbe reacted in a non-solvent system. In the case where a reaction solventhas to be removed, like a case where ASA-MA or ASA-DA is used in anaqueous system, the reaction is carried out preferably in thenon-solvent system.

With respect to the use amount of allylamine, diallylamine ormethallylamine, the equimolar amount based on a succinic anhydride groupof ASA is reacted. An amount less than the equimolar causes unreactedASA to remain, and amount exceeding the equimolar causes allylamines toform salts with a carboxyl group of ASA-DM or ASA-DA. Accordingly, bothare not preferred. Since allylamines are highly volatile, a closed typereaction vessel is preferably used. When the reaction is carried out inan open system, volatilized allylamines have to be trapped in a cooler.In such case, allylamines are added in advance in such an excess amountcorresponding to the amount of allylamines to be trapped that thereaction is completed. The reaction is carried out at atmosphericpressure or under pressure in a temperature range of 0 to 150° C.,preferably 5 to 130° C., and more preferably 10 to 100° C. for 30minutes to 10 hours, whereby intended ASA-MA or ASA-DA can be obtainedat a high yield. The reaction is an exothermic reaction, and thereaction temperature is controlled, if necessary, by heating or cooling.The temperature does not have to be maintained constant during thereaction, and the reaction temperature may be changed for the purpose ofcontrolling the reaction rate or adjusting the viscosity of the reactionliquid.

Both the raw material and the product of the allyl compound (1) of thepresent invention having a succinamide structure substituted with ahydrophobic group in the skeleton have polymerizable double bonds, andtherefore it is effective to use, if necessary, a polymerizationinhibitor in the production process. The polymerization inhibitorincludes phenols such as hydroquinone, hydroquinone monomethyl ether,hydroxyquinoline, methoxyphenol, and p-tert-butylcatechol, nitrocompounds such as nitrobenzol and nitropropane, nitroso compounds suchas N-nitrosodiphenylamine and cupferron, amines such as phenothiazine,p-phenylenediamine, N-diphenyl-p-phenylenediamine, and diphenylamine,stable radicals such as diphenylpicrylhydrazyl, galvinoxyl, pheldazyl,tri-p-nitrophenylmethyl, and di-p-fluorophenylamine, nitrous acidcompounds such as sodium nitrite, ethyl nitrite, and isopropyl nitrite,and in addition thereto, sulfur, copper salts, and thiourea compounds.The polymerization inhibitor is not restricted to the compoundsexemplified above, and they may be used alone or in combination of twoor more kinds thereof if necessary. The amount thereof is varieddepending on the polymerization inhibitors to be used, and it fallsusually in a range of 1 ppm to 300 weight %, preferably 50 ppm to 5weight % based on allylamines of the raw material.

The allyl compound (1) thus produced having a succinamide structuresubstituted with a hydrophobic group in the skeleton can be used in theform of the reaction solution after carrying out operations such asremoval of excess allylamines, but it can be separated, if necessary, bysimple operations such as removal of the solvent. When the intendedproduct having a high purity is required depending on uses, the allylcompounds which are solids at room temperatures such as those of whichhydrophobic groups are α-olefins can be recrystallized in a solvent suchas methanol, ethanol, isopropanol, acetone, toluene, benzene, xylene,and styrene. The allyl compounds which are liquid at room temperaturescan be subjected to refining treatment with a column by conventionalmethods.

The allyl compound (1) of the present invention having a succiniamidestructure substituted with a hydrophobic group in the skeleton can beproduced as well by amidation of succinic acid substituted with ahydrophobic group which is a hydrolysis product of ASA with allylamines,but it is more preferred in terms of the reactivity to use ASA as theraw material.

The allyl or vinyl compound (2) having a succinic acid ester structuresubstituted with a hydrophobic group in the skeleton is produced by thereaction of ASA with unsaturated alcohols, that is, allyl alcohol (AL),methallyl alcohol, 2-hydroxyethyl methacrylate (HM), 2-hydroxyethylacrylate (HA), 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate,3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxybutylmethacrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate,3-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutylacrylate, 4-hydroxypentyl methacrylate and 4-hydroxypentyl acrylate (thereaction products with ASA shall be hereinafter abbreviated as ASA-AL,ASA-HM and ASA-HA).

The reaction of ASA with unsaturated alcohols is usually carried out byadding dropwise unsaturated alcohols to an organic solvent solution ofASA while stirring. The organic solvents usable as a reaction solventmay be any ones as long as they dissolve both ASA and unsaturatedalcohols, and the examples thereof include acetone, 2-butanone, benzene,toluene, xylene, pentane, hexane, cyclohexane, DMF, DMSO, THF, diethylether, dioxane, dichloromethane, dichloroethane, and chloroform. Alcoholsolvents such as methanol, ethanol, isopropanol, methyl cellosolve,ethyl cellosolve, 2-ethylhexanol and cyclohexanol cause partialesterification with succinic anhydride in some cases and therefore arenot preferred. ASA which is liquid at room temperatures, such as ASAhaving a few carbon atoms and ASA using an internal olefin as a rawmaterial can be reacted in a non-solvent system. In the case where areaction solvent has to be removed, like a case where ASA-AL, ASA-HA orASA-HM is used in an aqueous system, the reaction is carried outpreferably in the non-solvent system.

The reaction proceeds without catalysts, but the catalysts arepreferably used in order to accelerate the reaction. The catalysts usedin the present reaction are not specifically restricted, and thecatalysts used for esterification can be used as well. To be concrete,the examples thereof include mineral acids such as sulfuric acid,hydrochloric acid and phosphoric acid; catalysts obtained by carryingthem on inorganic carriers such as silica; organic acids such asp-tolenesulfonic acid, methanesulfonic acid and benezenesulfonic acid;solid acids such as acid ion exchange resin, and in addition thereto,zinc chloride, sodium acetate, and pyridine. They can be used singly orin combination of two or more kinds thereof. The amount thereof can notdefinitely be specified since it is varied depending on the catalysts tobe used. Usually, it falls in a range of 0.001 to 300 weight %,preferably 0.01 to 30 weight % based on the weight of ASA of the rawmaterial.

Both the raw material and the product of the allyl or vinyl compound (2)used in the present invention having a succinic acid ester structuresubstituted with a hydrophobic group in the skeleton have polymerizabledouble bonds, and therefore it is effective to use, if necessary, apolymerization inhibitor in the production process. In particular,hydroxyalkyl (meth)acrylates such as HA and HM which are vinyl compoundsare highly polymerizable, and therefore polymerization inhibitors arepreferably used for the reaction. The same compounds as those used inproducing the allyl compound (1) having a succinamide structuresubstituted with a hydrophobic group in the skeleton can be used as thepolymerization inhibitor. The amount thereof is varied depending on thepolymerization inhibitors. Usually, it falls in a range of 1 ppm to 300weight %, preferably 50 ppm to 5 weight % based on the weight ofunsaturated alcohols of the raw materials.

The unsaturated alcohols are reacted in an equimolar amount based on asuccinic acid group of ASA (that is, a hydroxyl group of 1 mole per moleof acid anhydride in this case). An amount less than equimolar causesunreacted ASA to remain. An amount exceeding equimolar causes theunsaturated alcohols to remain and further provides the risk that thehydroxyl groups of the unsaturated alcohols react with the carboxylgroups of ASA-HA or ASA-HM in the presence of catalysts to form diestercompounds. Accordingly, both are not preferred.

The reaction is carried out at atmospheric pressure or under pressure ina temperature range of 0 to 150° C., preferably 5 to 130° C., and morepreferably 10 to 100° C. for 30 minutes to 20 hours, whereby intendedASA-AL, ASA-HA or ASA-HM can be obtained at a high yield. The reactionis an exothermic reaction, and the reaction temperature is controlled,if necessary, by heating or cooling. The temperature does not have to bemaintained constant during the reaction, and the reaction temperaturemay be changed for the purpose of controlling the reaction rate oradjusting the viscosity of the reaction liquid.

The allyl or vinyl compound (2) thus produced having a succinic acidester structure substituted with a hydrophobic group in the skeleton canbe used in the form of the reaction solution after carrying outoperations such as removal of excess unsaturated alcohols, but it can beseparated, if necessary, by simple operations such as removal of thesolvent. When the intended product having a high purity is requireddepending on uses, the compounds which are solids at room temperaturescan be recrystallized in a solvent such as methanol, ethanol,isopropanol, acetone, toluene, benzene, xylene, and styrene. The allylcompounds which are liquid at room temperatures can be subjected torefining treatment with a column by conventional methods.

The allyl or vinyl compound (2) used in the present invention having asuccinic acid ester structure substituted with a hydrophobic group inthe skeleton can be produced as well by esterification of a succinicacid derivative which is a hydrolysis product of ASA with unsaturatedalcohols, but it is more preferred in terms of the reactivity to use ASAas the raw material.

The amphipathic compounds (1) and (2) described above have carboxylgroups as hydrophilic groups in the molecules, and neutralization withalkali makes them dispersible or soluble in water. Among the amphipathiccompounds (1), the raw materials of the allyl compounds, such as ASA,having a succinamide structure substituted with a hydrophobic group ofan internal olefin in the skeleton have a low viscosity and are liquidcompounds, and the reaction can be carried out in a non-solvent system.However, since the compound itself produced by the reaction has a highviscosity, the viscosity of the reaction solution increases after thereaction, and therefore handling is difficult in some cases. Storingthis product at room temperatures for long time or subjecting it to heattreatment allows the imidization easily to form an N-allylsuccinimidecompound and therefore causes the amphipathic property to be lost insome cases. Accordingly, in the case where this compound is used in anaqueous solution system, since the advantages in handling that not onlythe imidization can be suppressed but also the viscosity can be reducedand that the solubility in water in the use is improved as well areinvolved, the reaction solution is preferably neutralized with alkalissuch as sodium hydroxide, potassium hydroxide and ammonia, or analkaline aqueous solution to turn the products into various salts anddiluted. The examples of the salts include salts of alkali metals suchas sodium, potassium and cesium, salts of alkaline earth metals such ascalcium and magnesium, salts of organic bases such as trimethylamine,dimethylamine, triethylamine, diethylamine, and pyridine, and ammoniumsalts. However, this compound is used without neutralization in the casewhere the polymerization is carried out in a non-aqueous solvent systemor in uses where the imidization is positively utilized. The allyl orvinyl compound (2), which is an amphipathic compound causing noimidization and having a relatively low viscosity, having a succinicacid ester structure substituted with a hydrophobic group of an internalolefin in the skeleton is neutralized immediately before using, in thecase where it is used in the form of a salt in an aqueous solution. A pHvalue at which the compound is dispersible or soluble in water is varieddepending on the kind and chain length of hydrophobic groups. Forexample, in the case of branched type ESA having 18 carbon atoms, the pHcondition is 8 or more, and the homogeneous polymerization withhydrophilic monomers using water as the solvent is possible. Theemulsion-polymerization can be carried out in the presence ofsurfactants even in a pH condition in which the compound is insoluble inwater, and the polymerization is possible as well in a solventdissolving both reactive surfactants and hydrophilic monomers.

The ethoxylate compound (3) obtained by reacting the allyl or vinylcompound having a succinamide or succinic acid ester structuresubstituted with a hydrophobic group in the skeleton with EO is obtainedby reacting the compound (1) or (2) with EO in the presence of an acidor base catalyst. The ethoxylate is expressed by adding EOA and anaverage addition mole number (n) to the abbreviation of the precursorcompound, for example, like ASA-AL-EOA (10). In the present invention,the ethoxylate is prepared by adding EO of 1 to 100 moles, preferably 2to 80 moles to the allyl or vinyl compound having a succinamide orsuccinic acid ester structure substituted with a hydrophobic group inthe skeleton.

Base catalysts or acid catalysts can be used as a catalyst for the EOaddition reaction. The examples of the base catalysts include sodiumhydroxide, potassium hydroxide and cesium hydroxide, and the examples ofthe acid catalysts include boron trifluoride ethyl ether complex. Thecatalysts are used in such an amount that when, for example, alkalimetal hydroxide is used as the base catalyst, the concentration of thecatalyst contained in the product after EO addition is 0.01 to 2 wt %,preferably 0.05 to 1 wt % in terms of the alkali metal hydroxide. Thecatalyst may remain in the product after finishing the reaction, but itis preferably neutralized with acid to adjust the pH to 4 to 10,preferably 5 to 9. The examples of the acid used for the neutralizationinclude inorganic acids such as phosphoric acid and sulfuric acid aswell as organic acids such as acetic acid and oxalic acid.

In a method for adding EO, the reaction is usually carried out byfeeding EO to a mixture of the allyl or vinyl compound having asuccinamide or succinic acid ester structure substituted with ahydrophobic group in the skeleton and the catalyst, and the reaction maybe carried out as well, if necessary, in the presence of solvents. Anysolvents can be used as the solvent suitable to the EO addition reactionas long as they do not have active hydrogens. The preferred examplesthereof include aromatic hydrocarbons such as benzene and toluene,aliphatic hydrocarbons such as cyclohexane and pentane, and aproticpolar solvents such as N,N-dimethyl-2-imidazolidinone anddimethylsulfolane.

The EO addition reaction is carried out at a reaction temperaturefalling in a range of 50 to 200° C., preferably 70 to 150° C. Thereaction is carried out at a reaction pressure falling in a range of 1to 100 kg/cm², preferably 2 to 50 kg/cm². The reaction time is settledso that the almost all amount of EO fed is consumed in the reaction, andit is usually 0.5 to 100 hours, preferably 1 to 50 hours.

Both the raw material and the product of the ethoxylate compound (3)used in the present invention, obtained by reacting the allyl or vinylcompound having a succinamide or succinic acid ester structuresubstituted with a hydrophobic group in the skeleton with EO havepolymerizable double bonds, and therefore it is effective to use, ifnecessary, a polymerization inhibitor in the production process. Inparticular, the derivatives of hydroxyalkyl (meth)acrylates such asASA-HA and ASA-HM which are vinyl compounds are highly polymerizable,and therefore polymerization inhibitors are preferably used for thereaction. The same compounds as those used in producing the allylcompound (1) having a succinamide structure substituted with ahydrophobic group in the skeleton can be used as the polymerizationinhibitor. The amount thereof is varied depending on the polymerizationinhibitors. Usually, it falls in a range of 1 ppm to 300 weight %,preferably 50 ppm to 5 weight % based on the weight of the allyl orvinyl compound having a succinamide or succinic acid ester structuresubstituted with a hydrophobic group in the skeleton, which is the rawmaterial.

The reaction can be carried out in any of a batch system, asemi-continuous system and a continuous system. When the reaction iscarried out in a batch system, a reactor is charged with the allyl orvinyl compound having a succinamide or succinic acid ester structuresubstituted with a hydrophobic group in the skeleton, the catalyst, andif necessary, the solvent, and the reaction is carried out while feedingEO continuously or semi-continuously. On the other hand, when thereaction is carried out in a continuous system, the reaction is carriedout while feeding continuously the allyl or vinyl compound having asuccinamide or succinic acid ester structure substituted with ahydrophobic group in the skeleton, EO, the catalyst, and if necessary,the solvent to the reactor. The product does not have to be specificallyrefined and can be the finished product as it is. However, in the casewhere the solvent is used, the finished product can be obtained afterseparating the solvent by operations such as distillation.

Since this compound group has a polyethylene oxide group (hereinafterabbreviated as a PEO group) as a hydrophilic group, the solubility inwater in a condition of a fixed temperature depends on the addition molenumber of EO to the hydrophobic groups. The EO addition mole numbergiving the water solubility is varied depending on the kind and thecarbon number of the hydrophobic group, and in the case of branched typeESA-AL having 18 carbon atoms, n is 11 or more in the conditions of 20°C. in pure water. Accordingly, some compounds of an ASA-AL-EOA type givewater solubility even in a neutral or acid condition of pH 8 or less,and therefore the polymerization is possible in an aqueous solvent in ahomogeneous system without a restriction of the pH condition.

Since ASA is an asymmetric compound, two position isomers are involvedin the preceding amphipathic compounds (1) to (3) having succinic acidsubstituted with a hydrophobic group as a base skeleton, and a mixtureof two kinds of the isomers is formed in ordinary reaction conditions.The presence of the respective isomers can be proved by detecting twokinds of corresponding carboxylic acid amide groups or carboxylic acidester groups by means of ¹ H-NMR and ¹³ C-NMR analytical methods.Allylamines or unsaturated alcohols are liable to form amide or esterbonds with carbons with which no hydrophobic groups are combined, and inthe case of, for example, allylamines, such tendency is notably observedin diallylamine rather than allylamine, and a hydrophobic group havingmany carbon atoms. These existential ratios are considered to depend ona chain length of a hydrophobic group of ASA, and reaction conditionssuch as a reaction solvent, a reaction temperature, and a reactionconcentration, but it is no problem to use both isomers withoutseparating for ordinary uses.

The allyl compound (4) having an amide structure of phthalic acid and aderivative thereof is produced by reacting carboxylic anhydride used asa raw material, such as phthalic anhydride, tetrahydrophthalicanhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalicanhydride, methylendomethylenetetrahydrophthalic anhydride, trimelliticanhydride, pyromellitic anhydride, chlorendic anhydride, andmethyltetrahydrophthalic anhydride with allylamine (MA), diallylamine(DA) or methallylamine.

The reaction of carboxylic anhydride with allylamine, diallylamine ormethallylamine is usually carried out by adding dropwise allylamine ordiallylamine to an organic solvent solution of carboxylic anhydridewhile stirring. The organic solvents usable as a reaction solvent may beany ones as long as they dissolve both carboxylic anhydrides andallylamines, and the examples thereof include acetone, 2-butanone,benzene, toluene, xylene, pentane, hexane, cyclohexane, DMF, DMSO, THF,diethyl ether, dioxane, dichloromethane, dichloroethane, and chloroform.Alcohol solvents such as methanol, ethanol, isopropanol, methylcellosolve, ethyl cellosolve, 2-ethylhexanol, and cyclohexanol causepartially esterification with carboxylic anhydride in some cases.However, since carboxylic anhydride is highly reactive with allylamines,and in general, ester is formed only in a small amount, alcohol solventscan be employed as well for uses in which mixing of esters do not exertgreat influences on the physical properties of the resins. Carboxylicanhydrides which are liquid at room temperatures can be reacted in anon-solvent system. In the case where the reaction solvent has to beremoved, like a case where the reaction product is used in an aqueoussystem, the reaction is carried out preferably in the non-solventsystem.

With respect to the amount of allylamine, diallylamine ormethallylamine, an equimolar amount based on a carboxylic anhydridegroup is reacted. An amount less than equimolar causes carboxylicanhydride to remain, and an amount exceeding equimolar causesallylamines to form salts with the carboxyl groups of the reactionproduct. Accordingly, both are not preferred. Since allylamines arehighly volatile, a closed type reaction vessel is preferably used. Whenthe reaction is carried out in an open system, volatilized allylamineshave to be trapped in a cooler. In such case, allylamines are added inadvance in such an excess amount corresponding to the amount ofallylamines to be trapped that the reaction is completed. The reactionis carried out at atmospheric pressure or under applying pressure in atemperature range of 0 to 150° C., preferably 5 to 130° C., and morepreferably 10 to 100° C. for 30 minutes to 10 hours, whereby thereaction product can be obtained at a high yield. The reaction is anexothermic reaction, and the reaction temperature is controlled, ifnecessary, by heating or cooling. The temperature does not have to bemaintained constant during the reaction, and the reaction temperaturemay be changed for the purpose of controlling the reaction rate oradjusting the viscosity of the reaction liquid.

Both the raw material and the product of the allyl compound (4) used inthe present invention having an amide structure of phthalic acid or aderivative thereof have polymerizable double bonds, and therefore it iseffective to use, if necessary, a polymerization inhibitor in theproduction process. The same compounds as those used in producing theallyl compound (1) having a succinamide structure substituted with ahydrophobic group in the skeleton can be used as the polymerizationinhibitor. The use amount thereof is varied depending on thepolymerization inhibitors to be used, and it falls usually in a range of1 ppm to 300 weight %, preferably 50 ppm to 5 weight % based on theweight of phthalic acid or a derivative thereof which is the rawmaterial.

The allyl compound (4) thus produced having an amide structure ofphthalic acid and a derivative thereof in the skeleton can be used inthe form of the reaction solution after carrying out operations such asremoval of excess allylamines, but it can be separated, if necessary, inthe form of a solid by a conventional method. The intended matter thusobtained can be used for various uses after providing simple operationssuch as removal of the solvent. When the product having a high purity isrequired depending on uses, the compounds can be recrystallized in asolvent such as methanol, ethanol, isopropanol, acetone, toluene,benzene, xylene, and styrene.

Further, the allyl compound (4) thus obtained having an amide structureof phthalic acid and a derivative thereof in the skeleton can beconverted to various salts by neutralizing carboxylic acids with variousbases for various purposes like providing water solubility. The examplesof the bases include salts of alkali metals such as sodium, potassiumand cesium, salts of alkaline earth metals such as calcium andmagnesium, salts of organic bases such as trimethylamine, dimethylamine,triethylamine, diethylamine, and pyridine, and ammonia. However, in thecase where this compound is polymerized in a non-aqueous solvent or inuses where imidization is positively utilized, it is used withoutneutralizing.

The allyl compound (4) of the present invention having an amidestructure of phthalic acid and a derivative thereof in the skeleton canbe produced as well by amidation of a hydrolysis product of a carboxylicanhydride group with allylamines, but carboxylic anhydride is preferablyused as the raw material in terms of the reactivity.

The allyl or vinyl compound (4) of the present invention having an esterstructure of a phthalic acid and a derivative thereof in the skeleton isa known compound and is produced by processes specified in the relatedarts. In general, it can be produced by the reaction of carboxylicanhydride with unsaturated alcohols as is the case with the allyl orvinyl compound (2) of the present invention having a succinic acid esterstructure substituted with a hydrophobic group in the skeleton.

The novel amphipathic compound groups of the present invention areuseful compounds used in many fields in the forms of modifiers forresins, additives, dispersants, and reactive surfactants.

The amphipathic compound used in the present invention has apolymerizable double bond and can be copolymerized with variousethylenically unsaturated compounds. The copolymer of the amphipathiccompound used in the present invention with the ethylenicallyunsaturated compound is a novel polymer. The polymer includes (I) awater soluble or dispersible amphipathic high molecular compoundproduced by copolymerizing the amphipathic compound with a hydrophilicethylenically unsaturated compound, (II) an emulsion produced by makinguse of the amphipatic compound as the reactive surfactant foremulsion-polymerization with a hydrophobic ethylenically unsaturatedcompound, (III) an amphipathic high molecular compound produced bycopolymerizing the amphipathic compound with a hydrophilic nonionicethylenically unsaturated compound in the presence of a colloidizingagent, and (IV) an emulsion produced by using the amphipathic highmolecular compound (I) or (III) as a dispersant.

The ethylenically unsaturated compound used in the present invention isclassified as follows, and the examples of the respective compounds tobe used shall be given in advance. The ethylenically unsaturatedcompound includes a hydrophilic ethylenically unsaturated compound and ahydrophobic ethylenically unsaturated compound.

The hydrophilic ethylenically unsaturated compound is classified into anonionic ethylenically unsaturated compound and an ionic ethylenicallyunsaturated compound, and the hydrophilic ethylenically unsaturatedcompound is at least one compound selected from each group.

The hydrophilic nonionic ethylenically unsaturated compound isclassified into an unsaturated carboxylic acid amide compound, ahydrophilic nonionic vinyl compound, and a hydrophilic nonionic allylcompound, and the hydrophilic nonionic ethylenically unsaturatedcompound is at least one compound selected from each group.

The examples of the unsaturated carboxylic acid amide compound includeacrylamide, methacrylamide, diacetoneacrylamide, N-methylacrylamide,N-methylmethacrylamide, N,N-dimethylacrylamide,N,N-dimethylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide,N,N-diethylacrylamide, N,N-diethylmethacrylamide, N-propylacrylamide,N-acryloylpyrrolidine, N-acryloylpiperidine, N-acryloylmorpholine,N,N-di-n-propylacrylamide, N-n-butylacrylamide, N-n-hexylacrylamide,N-n-hexylmethacrylamide, N-n-octylacrylamide, N-n-octylmethacrylamide,N-tert-octylacrylamide, N-dodecylacrylamide, N-n-dodecylmethacrylamide,N,N-diglycidylacrylamide, N,N-diglycidylmethacrylamide,N-(4-glycidoxybutyl)acrylamide, N-(4-glycidoxybutyl)methacrylamide,N-(5-glycidoxypentyl)acrylamide, N-(6-glycidoxyhexyl)acrylamide,methylenebisacrylamide, N,N'-ethylenebisacrylamide,N,N'-hexamethylenebisacrylamide, and N-methylolacrylamide.

The hydrophilic nonionic vinyl compound includes N-vinyl-2-pyrrolidone,N-vinylformamide, N-vinylacetamide, N-vinyloxazolidone,N-vinyl-5-methyloxazolidone, N-vinylsuccinimide, 2-hydroxyethylacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate,3-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, and2-hydroxypropyl methacrylate. Further, the hydrophilic nonionic allylcompound includes allyl alcohol and methallyl alcohol.

The hydrophilic ionic ethylenically unsaturated compound is classifiedinto an unsaturated carboxylic acid compound, an ionic vinyl compoundand an ionic allyl compound, and the hydrophilic ionic ethylenicallyunsaturated compound is at least one compound selected from each group.

The examples of the unsaturated carboxylic acid compound include acidssuch as acrylic acid, methacrylic acid, crotonic acid, angelic acid,tiglic acid, 2-pentenoic acid, β-methylcrotonic acid, β-methyltiglicacid, α-methyl-2-pentenoic acid, β-methyl-2-pentenoic acid, maleic acid,fumaric acid, maleic anhydride, itaconic acid, citraconic acid,mesaconic acid, glutaconic acid, α-dihydromuconic acid,2,3-dimethylmaleic acid, 2-methylglutaconic acid, 3-methylglutaconicacid, 2-methyl-α-dihydromuconic acid and 2,3-dimethyl-α-dihydromuconicacid, and alkali metal salts, ammonium salts and organic amine saltsthereof.

The ionic vinyl compound includes sulfonic acids such as vinylsulfonicacid, styrenesulfonic acid, 2-acrylamide-2-phenylpropanesulfonic acid,2-acrylamide-2-methylpropanesulfonic acid and 2-sulfoethylacrylate, andalkali metal salts, ammonium salts and organic amine salts thereof,cationic vinyl compounds such as N,N-dimethylaminoethylacrylate (DA),N,N-dimethylaminoethylmethacrylate (DM),N,N-dimethylaminopropylacrylamide (DMAPAA) andN,N-dimethylaminopropylmethacrylamide (DMAPMA), and vinyl compoundsobtained by quaternarizing DA, DM, DMAPAA and DMAPMA with dimethylsulfate, halogenated alkyls such as methyl chloride and methyl bromide,allyl chloride, halogenated benzyls such as benzyl chloride and benzylbromide, epihalohydrins such as epichlorohydrin and epibromohydrin, andepoxides such as propylene oxide and styrene oxide.

The ionic allyl compound includes allylamines such as allylamine,N-methylallylamine, 2-methylallylamine, diallylamine, anddimethyldiallylammonium chloride, and salts thereof, allylsulfonic acidssuch as allylsulfonic acid and methallylsulfonic acid, and saltsthereof.

The hydrophobic ethylenically unsaturated compound is at least onecompound selected from the group consisting of aromatic vinyl compounds,cyanized vinyl compounds, diene compounds, unsaturated carboxylic acidester compounds, vinyl alkyl ether compounds, other ethylenicallyunsaturated compounds and hydrophobic allyl compounds.

The aromatic vinyl compound includes styrene, α-methylstyrene,α-chlorostyrene, p-tert-butylstyrene, p-methylstyrene, p-chlorostyrene,o-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene anddivinylbenzene.

The cyanized vinyl compound includes acrylonitrile, methacrylonitrileand α-chloro-acrylonitrile.

The diene compound includes diolefin compounds such as butadiene,isoprene, allene and 2-chloro-1,3-butadiene, and chloroprene.

The unsaturated carboxylic acid ester compound includes methyl acrylate,methyl methacrylate, ethyl acrylate, ethyl methacrylate, propylacrylate, propyl methacrylate, butyl acrylate, butyl methacrylate,lauryl acrylate, lauryl methacrylate, benzyl acrylate, benzylmethacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycidylacrylate, glycidyl methacrylate, (di)methyl maleate, (di)ethyl maleate,(di)butyl maleate, (di)methyl fumarate, (di)ethyl fumarate, (di)butylfumarate, (di)methyl itaconate, (di)ethyl itaconate, (di)butylitaconate, ethyleneglycol diacrylate, ethyleneglycol dimethacrylate,diethyleneglycol diacrylate, diethyleneglycol dimethacrylate,triethyleneglycol diacrylate, triethyleneglycol dimethacrylate,tetraethyleneglycol dimethacrylate, polyethyleneglycol (meth)acrylate,1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediolacrylate, methoxypolyethyleneglycol (meth)acrylate,ethoxypolyethyleneglycol (meth)acrylate, propoxypolyethyleneglycol(meth)acrylate, isopropoxypolyethyleneglycol (meth)acrylate,phenoxypolyethyleneglycol (meth)acrylate, and unsaturated carboxylicacid ester compounds of epoxy acrylates and urethane acrylates.

The vinyl alkyl ether compound includes vinyl methyl ether, vinyl ethylether, vinyl isopropyl ether, vinyl n-propyl ether, vinyl isobutylether, vinyl 2-ethylhexyl ether and vinyl n-octadecyl ether.

The other ethylenically unsaturated compounds include vinyl acetate,vinyl propionate, vinyl chloride, vinylidene chloride, α-olefins(ethylene, propylene and butene, etc.), divinyl esters such as divinyladipate and divinyl sebacate, maleimide, N-phenylmaleimide andN-cyclohexylmaleimide.

Further, the hydrophobic allyl compounds include diallyl isophthalate,diallyl terephthalate, diethyleneglycol diallylcarbonate andtriallylcyanurate.

Polymerization initiators used in the present invention include watersoluble initiators and oil soluble initiators, and the examples of therespective initiators shall be given in advance.

The water soluble polymerization initiators of peroxides include, forexample, ammonium persulfate, potassium persulfate, hydrogen peroxide,and tert-butyl peroxide. In this case, they can be used either singly orin the form of redox initiators by combining with reducing agents. Therecan be used as the reducing agents, for example, sulfites,hydrogensulfites, salts of low valency metals of iron, copper andcobalt, etc., hypophosphorous acid, hypophosphites, organic amines suchas N,N,N',N'-tetramethylethylenediamine and reducing sugars such asaldose and ketose. The azo compound initiators include2,2'-azobis-2-amidinopropane hydrochloride,2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleic acidand salts thereof. Further, the polymerization initiators describedabove may be used in combination of two or more kinds thereof.

The addition amount of the polymerization initiators falls in a range of0.0001 to 10 weight %, preferably 0.01 to 8 weight % based on the weightof monomers. In the case of the redox initiators, the addition amount ofthe reducing agents is 0.1 to 100 %, preferably 0.2 to 80 % based onmoles of the polymerization initiators.

The oil soluble initiators of the peroxides include benzoyl peroxide,dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl-peroxide,1,1,3,3-tetramethylbutyl peroxide,2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, tert-butylperbenzoate, tert-butyl peracetate, tert-butyl perphenylacetate,tert-butyl peroxylaurate and cumyl perpivalate. The azo compoundinitiators include azobisisobutyronitrile,2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),2,2'-azobis(2,4-dimethyl-valeronitrile), 2,2'-azobisisobutyronitrile,1,1'-azobis(cyclohexane-1-carbonitrile),2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile,2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane) anddimethyl 2,2'-azobis(2-methylpropionate). Further, the polymerizationinitiators described above can be used in combination of two or morekinds thereof.

The addition amount of the polymerization initiators falls in a range of0.0001 to 10 weight %, preferably 0.01 to 8 weight % based on the weightof monomers.

In the polymerization reaction of the present invention, chain transferagents and if necessary, pH controllers may be added for the purpose ofcontrolling the molecular weight or the polymerization rate, and theexamples of the respective compounds shall be given in advance.

The chain transfer agents include water soluble chain transfer agentsand oil soluble chain transfer agents. The water soluble chain transferagents include isopropyl alcohol, α-thioglycerol, mercaptosuccinic acid,thioglycolic acid, triethylamine and sodium hypophosphite. They aresuitably used singly or in a mixture of two or more kinds thereof. Theoil soluble chain transfer agents include mercaptans such ashexylmercaptan octylmercaptan, dodecylmercaptan, tetradecylmercaptan,cetylmercaptan, and stearylmercaptan, xanthogene disulfides such asdimethylxanthogene disulfide, diethylxanthogene disulfide, anddiisopropylxanthogene disulfide, thiuram disulfides such astertamethylthiuram disulfide, tertaethylthiuram disulfide, andtertabutylthiuram disulfide, terpenoids such as terpinolene,α-methylstyrene dimer, 2-ethylhexyl thioglycolate, 3-phenyl-l-pentene,1,4-cyclohexadiene, hydroquinone, t-butylcatechol,2,6-di-tert-butyl-4-methylphenol, 2,6-xylenol, cysteamine, sulfur, andnitroso compounds. They can suitably be used singly or in a mixture oftwo or more kinds thereof. The pH controllers include inorganic acidssuch as hydrochloric acid, sulfuric acid, phosphoric acid, and boricacid, organic acids such as formic acid, acetic acid, succinic acid,citric acid, tartaric acid and L-ascorbic acid, inorganic bases such assodium hydroxide, potassium hydroxide and ammonia, organic bases such asethanolamine, trimethylamine and triethylamine, and salts such as sodiumhydrogencarbonate, sodium carbonate, sodium acetate and sodiumdihydrogenphosphate. Further, for the purposes of masking metal ions andcontrolling the polymerization rate, there may be used in combination,compounds such as sodium ethylenediaminetetraacetate (EDTA-Na), citricacid, tartaric acid, urea, thiourea, L-ascorbic acid,ethylenetrithiocarbonate, phenothiazine and nicotinic acid amide. Theamounts of the pH controllers, the chain transfer agents, the metalmasking agents and the polymerization rate controllers are varieddepending on use. In general, the amount of the pH controllers falls ina range of 100 ppm to 10%, and the amounts of the chain transfer agentsand the other additives fall in a range of 1.0 ppm to 5.0% each based onthe weight of the monomers.

A method for polymerizing the amphipathic compound used in the presentinvention with the ethylenically unsaturated compound is notspecifically restricted, and the polymerization can be carried out byknown methods. Usually, the polymerization is carried out by maintainingprescribed temperatures in the presence of a radical polymerizationinitiator. The temperature does not have to be maintained at the sametemperature during the polymerization and may suitably be changed as thepolymerization goes on. The polymerization can be carried out whileheating or cooling, if necessary. The polymerization temperature isvaried depending on the kinds of the monomers and the polymerizationinitiators to be used. In the case of the single initiator, thepolymerization temperature falls usually in a range of 30 to 200° C. Onthe other hand, in the case of the redox polymerization initiators, thetemperature is lowered; when the redox polymerization is carried out inone lot, the temperature is usually -5 to 50° C.; and in the redoxpolymerization case where the components are added consecutively, thetemperature is usually 30 to 90° C. When the amphipathic compoundshaving a succinamide skelton or phthalic amide skeleton are used in theacidic form (M in (1)-(4), (18)-(21) is a hydrogen atom), imidecyclization caused by dehydration may take place at high temperatures of100° C. or higher, but no specific problems are involved in the casewhere the application to heat resistant resins is intended. Anatmosphere in a polymerization vessel is not specifically restricted.For the purpose of carrying out rapidly the polymerization, theatmosphere is preferably substituted with inert gas such as nitrogengas. The polymerization time is not specifically limited and is usually1 to 40 hours.

Any solvents may be used as a polymerization solvent as long as theydissolve homogeneously the amphipathic compound and the ethylenicallyunsaturated compound used in the present invention. The examples oforganic solvents include hexane, cyclohexane, decalin, tetralin,dioxane, carbon tetrachloride, benzene, toluene, xylene, cumene,ethylbenzene, carbon disulfide, chloroform, ethyl acetate, acetic acid,morpholine, tetrahydrofuran, pyridine, methyl ethyl ketone, acetone,alcohols such as methanol, ethanol, propanol, butanol, methylcellosolve, ethyl cellosolve, butyl cellosolve and ethylene glycol,formamide, dimethylformamide, and dimethylsulfoxide. In particular, inuses where the solvents have to be removed after the polymerization, thecopolymerization of the amphipatic compound with the ethylenicallyunsaturated compound which is compatible or miscible with theamphipathic compound used in the present invention is preferably carriedout in a non-solvent system in some cases for the purpose of simplifyingthe process. The uses of the high molecular compound produced bypolymerization in a non-aqueous system include plasticizers, heatresistant resins, antistatic resins, lubricants, paints, adhesives,dispersants, surfactants, and admixtures for cement.

The amphipathic compound used in the present invention has aparticularly high utility value as a raw material used for producingwater soluble or dispersible amphipathic compounds or water dispersibleresins. The examples thereof shall concretely be explained in (I), (II),(III) and (IV).

(I) The amphipathic compound used in the present invention can behomogeneously copolymerized with the hydrophilic ethylenicallyunsaturated compound using water as the solvent on pH and temperatureconditions that the amphipathic compound is water soluble, whereby thewater soluble or dispersible amphipathic high molecular compound (I) canbe produced. The amphipathic compound can be emulsion-polymerized in thepresence of surfactants even on pH and temperature conditions that theamphipathic compound is insoluble in water. This amphipathic highmolecular compound (I) can be produced by copolymerizing the amphipathiccompound represented by any of Formulas (5) to (8), Formulas (18) to(21) and Formulas (22) to (25), or a mixture thereof with thehydrophilic ethylenically unsaturated compound in an aqueous solvent byknown methods. Usually, the polymerization is carried out by maintainingthe polymerizing solution at prescribed temperatures in the presence ofa radical polymerization initiator. The temperature does not have to bemaintained at the same temperature during the polymerization and maysuitably be changed as the polymerization goes on. The polymerization iscarried out while heating or cooling, if necessary. The polymerizationtemperature is varied depending on the kinds of the monomers and thepolymerization initiators to be used. In the case of the singleinitiator, the polymerization temperature falls usually in a range of 30to 100° C. On the other hand, in the case of the redox polymerizationinitiators, the temperature is lowered; when the redox polymerization iscarried out in one lot, the temperature is usually -5 to 50° C.; and inthe redox polymerization case where the components are addedconsecutively, the temperature is usually 30 to 90° C. An atmosphere ina polymerization vessel is not specifically restricted. For the purposeof carrying out rapidly the polymerization, the atmosphere is preferablysubstituted with inert gas such as nitrogen gas. The polymerization timeis not specifically limited and is usually 1 to 40 hours.

Water is used for a polymerization solvent, and organic solvents such asmethanol, ethanol, isopropanol, acetone, ethylene glycol, and propyleneglycol may be used in combination. The amphipathic compound, themonomers, the solvent, the polymerization initiator, and the chaintransfer agent which all are used for the polymerization may be chargedinto a reaction vessel in one lot at the time when the polymerizationstarts, or one or more components may be added singly or in the form ofa mixture thereof with the solvent consecutively as the polymerizationproceeds.

In producing the amphipathic high molecular compound (I) bycopolymerizing the amphipathic compound with the hydrophilicethylenically unsaturated compound, a hydrophobic ethylenicallyunsaturated compound may be used as a copolymerizable component for thepurpose of increasing the hydrophobicity. In this case, an excess amountof the hydrophobic ethylenically unsaturated compound used causes aproblem that the water dispersibility of the amphipathic high molecularcompound substantially disappeared and that the particles of thehydrophobic resin dispersed only by the amphipathic compound as theemulsifier are formed. Accordingly, in general, the amount of thehydrophobic ethylenically unsaturated compound is preferably 30% or lessbased on the hydrophilic ethylenically unsaturated compound.

In general, the amphipathic high molecular compound (I) of the presentinvention thus obtained is suitably used for plasticizers, heatresistant resins, antistatic agents, lubricants, paints, adhesives,dispersants, thickeners, high molecular surfactants and admixtures forcement. In particular, it can preferably be used for a paper makingadditive containing the above compound as an effective ingredient. Amongthem, the amphipathic high molecular compound (I) of the presentinvention, which is soluble or dispersible in water, has a high utilityvalue as a novel sizing agent which can improve paper reinforcingperformance.

The amphipathic high molecular compound (I) of the present invention hasa viscosity falling in a range of 0.01 to 500 poise at a concentrationof 5 to 30 weight % at 25° C. Since the amphipathic high molecularcompound (I) of the present invention is water dispersible in itselfunlike ASA and other phthalic acid group compounds which are thestarting materials, it does not have to be emulsified with surfactantsand can be used as it is.

(II) The amphipathic compound used in the present invention is a usefulcompound as a reactive surfactant, and a water dispersible type resincomposition (II) produced by emulsion-polymerizing the above reactivesurfactant with the ethylenically unsaturated compound has an ability toform a polymer film which is particularly excellent in heat resistanceand water resistance. That is, the water dispersible type resincomposition (II) is obtained by emulsion-polymerizing the reactivesurfactant represented by any of Formulas (5) to (8), Formulas (18) to(21) and Formulas (22) to (25), or a mixture thereof [A] of 0.1 to 50weight % with the ethylenically unsaturated compound [B] of 50 to 99.9weight %.

A hydrophobic ethylenically unsaturated compound is mainly used for theethylenically unsaturated compound. However, a hydrophilic ethylenicallyunsaturated compound which is usually used for the purpose of improvingthe stability of polymers may be added in the polymerization. The amountthereof falls usually in a range of 0.1 to 20 weight % based on theweight of the hydrophobic ethylenically unsaturated compound.

The polymerized amounts of the reactive surfactant [A] and theemulsion-polymerizable ethylenically unsaturated compound [B] fallusually in a range of 0.1 to 20 weight % for [A] and 80 to 99.9 weight %for [B], preferably 0.5 to 10 weight % for [A] and 90 to 99.5 weight %for [B] based on the total weight of the whole monomers. An amount of[A] of less than 0.1 weight % lowers the emulsification stability of theresin composition of the present invention, and the amount exceeding 20weight % reduces the water resistance of a dried film of the resincomposition.

The water dispersible type resin composition (II) of the presentinvention can be produced by known emulsion-polymerization methods inthe presence of a pH controller, a chain transfer agent, a metal maskingagent, and a protective colloid agent according to necessity.

There can be used as the protective colloid agent, partially saponifiedpolyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose andacrylamide. In general, the amount of the protective colloid agent fallsin a range of 0.1 to 20%, preferably 0.1 to 10% based on the wholeamount of the monomers.

A method for emulsion-polymerizing the ethylenically unsaturatedcompound is not specifically restricted, and the polymerization can becarried out by known methods. Usually, the polymerization is carried outby maintaining the polymerizing solution at prescribed temperatures inthe presence of a radical polymerization initiator. The temperature doesnot have to-be maintained at the same temperature during thepolymerization and may suitably be changed as the polymerization goeson. The polymerization is carried out while heating or cooling, ifnecessary. The polymerization temperature is varied depending on thekinds of the monomers and the polymerization initiators to be used. Inthe case of the single initiator, the polymerization temperature fallsusually in a range of 30 to 200° C. On the other hand, in the case ofthe redox polymerization initiators, the temperature is lowered; whenthe redox polymerization is carried out in one lot, the temperature isusually -5 to 50° C.; and in the redox polymerization case where thecomponents are added consecutively, the temperature is usually 30 to 90°C. An atmosphere in a polymerization vessel is not specificallyrestricted. For the purpose of carrying out rapidly the polymerization,the atmosphere is preferably substituted with inert gas such as nitrogengas. The polymerization time is not specifically limited and is usually1 to 40 hours.

Water is used for a polymerization solvent, and organic solvents such asmethanol, ethanol, isopropanol, acetone, ethylene glycol, and propyleneglycol may be used in combination.

The reactive surfactant, the ethylenically unsaturated compound, thepolymerization initiator, the solvent, and the chain transfer agentwhich are-used for the polymerization may be charged into a reactionvessel in one lot at the time when the polymerization starts, or one ormore components may be added singly or in the form of a mixture thereofwith the solvent, for example, an emulsion solution of the ethylenicallyunsaturated compound, consecutively as the polymerization proceeds.

The reactive surfactant of a type having a carboxyl group, representedby any of Formulas (18) to (21) and Formulas (22) to (25) is usuallyused in the form of a salt. In addition, possible is a method in whichthe reactive surfactant is dissolved in the hydrophobic ethylenicallyunsaturated compound or a mixture containing the hydrophobicethylenically unsaturated compound without neutralizing the carboxylgroup to carry out the emulsion-polymerization on a weak acidic toneutral condition. However, in this case the polymerization system isunstable, and coagulated matters are liable to be formed. Effective forpreventing this are a method in which the polymerization is carried outwhile neutralizing by adding alkali to the polymerization system and amethod in which known surfactants are used in combination. When alkaliis not added, it is preferred from the viewpoint of stabilizing theemulsion to neutralize the carboxyl group by adding alkali after theemulsion-polymerization. However, in order to enhance the heatresistance, the emulsion may be used without neutralization.

The reactive surfactant contained in the emulsion thus obtained isusually in the form of a carboxylic acid salt and contributes to thestabilization of the emulsion. A polymer film produced from thisemulsion is improved in water resistance as compared with the case wherea non-polymerizable surfactant is used. If the film is subjected to acidtreatment and then to heat treatment, the water resistance is furtherimproved, and the heat resistance is enhanced as well. Acid used for theacid treatment is either or both of an inorganic acid such ashydrochloric acid, sulfuric acid and phosphoric acid and an organic acidsuch as formic acid, acetic acid and citric acid. The heat treatmenttemperature and time can suitably be changed depending on the filmthickness and the polymer composition, and the heat treatment is usuallycarried out in the ranges of 80 to 150° C. and of some seconds to someten minutes. The heat treatment is carried out in the air or an inertgas such as nitrogen and argon.

The water dispersible type resin composition (II) of the presentinvention may further contain, if necessary, additives such aspreservatives, defoaming agents, cross-linking agents, viscositycontrollers, film forming aids, plasticizers, antistatic agents,sticking agents, freezing stabilizers, pigments, fillers and dyes.

The water dispersible resin composition (II) of the present invention isused in the fields of plasticizers, heat resistant resins, antistaticresins, lubricants, paints, adhesives, additives for cement and papermaking additives.

(III) The amphipathic high molecular compound can be synthesized bycopolymerizing the reactive surfactant with the hydrophilic, nonionicethylenically unsaturated compound. In such amphipathic high molecularcompound, interaction works between the hydrophobic groups in an aqueousmedium, and therefore a high molecular micelle structure is formed insuch a low concentration range as 1% or less. However, on the conditionof an increase in the molecular weight of the amphipathic high molecularcompound or an increase in the solution concentration, hydrophobic groupinteraction comes to work between the molecules of the amphipathic highmolecular compound, and therefore the solution viscosity increasesmarkedly. Known is a technique in which the amphipathic high molecularcompound is used as a thickener of an association type for improvingrheology of aqueous paint and synthetic latex utilizing such property.

However, in the cases where the viscosity of the aqueous solution doesnot have to be increased, for example, in the case where the amphipathichigh molecular compound is used for dispersing hydrophobic compounds asa high molecular surfactant, or in the case where it is used for papermaking additives such as a sizing agent, such thickening effect asdescribed above is not preferred in some cases. That is, in such uses,the amphipathic high molecular compound is transported or usedpreferably in the form of an aqueous solution. However, an increase inthe molecular weight of the amphipathic high molecular compound resultsin higher solution viscosity, and to a large extent causing the fluidityto be lost, thereby making handling difficult. While the polymerizationcarried out in the lowered concentration produces the high molecularcompound of a high molecular weight, there has been a problem that fromthe view point of production efficiency and the transportationefficiency, there exists a fixed upper limit in the molecular weight ofthe amphipathic high molecular compound which can be substantiallyproduced, depending on the concentration of the amphipathic highmolecular compound.

In the copolymerization of the reactive surfactant used in the presentinvention with the hydrophilic, nonionic ethylenically unsaturatedcompound, it has been found that the amphipathic high molecular compoundhaving a higher molecular weight and a lower viscosity in an aqueoussolution, as compared with those in conventional methods, can beproduced by adding continuously or intermittently a compound(hereinafter referred to as a "colloidizing agent") having an ability tosubstantially lower the solubility of the reactive surfactant in water.

The present invention relates to a process for producing the amphipathichigh molecular compound (III), characterized by that the reactivesurfactant represented by Formulas (5) to (8), Formulas (18) to (21) andFormulas (22) to (25) is copolymerized with the hydrophilic, nonionicethylenically unsaturated compound in the presence of the colloidizingagent.

That is, the amphipathic high molecular compound (III) can be producedby copolymerizing the above reactive surfactant of 0.1 to 90 weight %with the hydrophilic, nonionic ethylenically unsaturated compound of 10to 99.9 weight % in the presence of the colloidizing agent of 0.1 to 10moles per mole of the reactive surfactant.

The colloidizing agent is a compound having an ability to lower thesolubility in water of the above reactive surfactant, and the examplesof the colloidizing agent are classified into compound groups ofinorganic acids, organic acids, inorganic bases, organic bases, andsalts of the respective acids and bases described above. Thecolloidizing agents are used singly or in optional combination of two ormore kinds thereof. The colloidizing agent is used in a range of 0.1 to10 moles, preferably 0.2 to 5 moles per mole of the reactive surfactant.

The examples of inorganic acids include hydrochloric acid, nitric acid,sulfuric acid, phosphoric acid, and boric acid. The examples of theorganic acids include carboxylic acid compounds such as formic acid,acetic acid, succinic acid, citric acid, tartaric acid, L-ascorbic acid,and unsaturated carboxylic acid compounds such as acrylic acid,methacrylic acid, crotonic acid, angelic acid, tiglic acid, 2-pentenoicacid, β-methylcrotonic acid, β-methyltiglic acid, α-methyl-2-pentenoicacid, β-methyl-2-pentenoic acid, maleic acid, fumaric acid, maleicanhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconicacid, α-dihydromuconic acid, 2,3-dimethylmaleic acid, 2-methylglutaconicacid, 3-methylglutaconic acid, 2-methyl-α-dihydromuconic acid and2,3-dimethyl-α-dihydromuconic acid, and unsaturated sulfonic acidcompounds such as vinylsulfonic acid, styrenesulfonic acid,2-acrylamide-2-phenylpropanesulfonic acid,2-acrylamide-2-methylpropanesulfonic acid, allylsulfonic acid andmethallylsulfonic acid.

The examples of the inorganic bases include lithium hydroxide, sodiumhydroxide, potassium hydroxide, sodium carbonate, sodiumhydrogencarbonate and ammonia. The examples of the organic bases includehydrazine, ethylenediamine, ethanolamine, dimethylamine, diethylamine,trimethylamine, triethylamine and salts thereof, basic vinyl compoundssuch as N,N-dimethylamino ethylacrylate (DA), N,N-dimethylaminoethylmethacrylate (DM), N,N,-dimethylamino ethylacrylate, N,N-dimethylaminoethylmethacrylate, N,N-diethylaminoethyl acrylate, N,N-diethylaminoethylmethacrylate, N,N-dimethylaminopropylacrylamide (DMAPAA),N,N-dimethylaminopropylmethacrylamide (DMAPMA) and salts thereof, andallylamines such as allylamine, N-methylallylamine, 2-methylallylamine,and diallylamine and salts thereof. Further included are vinyl compoundsobtained by quaternizing DA, DM, DMAPAA and DMAPMA with dimethylsulfate, halogenated alkyls such as methyl chloride and methyl bromide,allyl chloride, halogenated benzyls such as benzyl chloride and benzylbromide, epihalohydrins such as epichlorohydrin and epibromohydrin, andepoxides such as propylene oxide and styrene oxide, anddimethyldiallylammonium chloride.

The amphipathic high molecular compound (III) of the present inventioncan be produced by copolymerizing the reactive surfactant with thehydrophilic, nonionic ethylenically unsaturated compound in an aqueousmedium by known methods while adding continuously or intermittently theabove colloidizing agent. Usually, the polymerization is carried out bymaintaining the polymerizing solution at prescribed temperatures in thepresence of a radical polymerization initiator. The temperature does nothave to be maintained at the same temperature during the polymerizationand may suitably be changed as the polymerization goes on. Thepolymerization is carried out while heating or cooling, if necessary.The polymerization temperature is varied depending on the kinds of theethylenically unsaturated compound and the polymerization initiators tobe used. In the case of the single initiator, the polymerizationtemperature falls usually in a range of 30 to 100° C. On the other hand,in the case of a redox polymerization initiators, the temperature islowered; when the redox polymerization is carried out in one lot, thetemperature is usually -5 to 50° C.; and in the redox polymerizationcase where the components are added consecutively, the temperature isusually 30 to 90° C. An atmosphere in a polymerization vessel is notspecifically restricted. For the purpose of carrying out rapidly thepolymerization, the atmosphere is preferably substituted with inert gassuch as nitrogen gas. The polymerization time is not specificallylimited and is usually 1 to 40 hours.

Water is used as a polymerization solvent, and organic solvents such asmethanol, ethanol, isopropanol, acetone, ethylene glycol, and propyleneglycol may be used in combination.

The amphipathic high molecular compound (III) of the present inventioncan be produced by using a pH controller, a chain transfer agent, and ametal masking agent, if necessary.

The reactive surfactant, the ethylenically unsaturated compound, thesolvent, the polymerization initiator, and the chain transfer agentwhich all are used for the polymerization may be charged into a reactionvessel in one lot at the time when the polymerization starts, or one ormore components may be added singly or in the form of a mixture thereofwith the solvent consecutively as the polymerization proceeds. Thecolloidizing agent may be blended with the addition solution but has tobe so added separately that the reactive surfactant and the colloidizingagent are not contained in the same solution. Further, in the case ofthe reactive surfactant having a carboxyl group before thepolymerization, a pH of the solution is adjusted to 7 or more with the apH controller that the carboxyl group is turned into the alkali metalsalt or ammonium salt. The colloidizing agent is usually addedcontinuously or intermittently in 10 minutes to 40 hours, and thereactive surfactant has to be charged into the reaction vessel at leastbefore finishing the addition of the colloidizing agent.

The amphipathic high molecular compound (III) of the present inventionmay further contain, if necessary, preservatives, defoaming agents,cross-linking agents, viscosity controllers, film forming aids,plasticizers, antistatic agents, sticking agents, freezing stabilizers,pigments, fillers, and dyes.

The amphipathic high molecular compound (III) thus obtained ischaracterized by a higher molecular weight and a viscosity reduced to alarge extent in the same concentration as compared with those of theamphipathic high molecular compound (I), and it is used in the fields ofplasticizers, heat resistant resins, antistatic agents, lubricants,paints, adhesives, admixtures of cement and paper making additives, andfor uses in which high molecular surfactants are used.

(IV) Known is a technique in which functional groups are introduced onthe surface of the particles of a high molecular emulsion to controlreactivity and charging state on the surface of the emulsion and toimprove a mechanical stability of the emulsion. Further, as a method inwhich highly hydrophilic functional groups are caused to be distributedon the surface phase of emulsion particles, known is a method in which ahydrophilic ethylenically unsaturated compound and a hydrophobicethylenically unsaturated compound are copolymerized by soap-freeemulsion polymerization. However, involved in this method is the problemthat while heteromorphologic structure particles in which a highlyhydrophilic ethylenically unsaturated compound unit is distributed onthe surface phase thereof are naturally formed, the amount of thehydrophilic high molecular compound eluted in the aqueous phase in thepolymerization process without staying on the particle surface can notbe ignored, and therefore the intended particles can not efficiently beproduced.

Further, known is a method in which particles having a heteromorphologicstructure are produced with a hydrophilic high molecular compound usedas a seed. It is known that in this case, a distribution in ahydrophobic high molecular compound after polymerization is affected toa large extent by the cross-linking degree of the seed particles and anincrease in the cross-linking degree usually causes a hydrophobic highmolecular phase to be distributed in the vicinity of the particlesurface. On the other hand, there is the problem that in the case wherea hydrophilic high molecular compound having a low cross-linking degreeis used for the seed, the amount of the hydrophilic high molecularcompound which is present free from particles can not be ignored.

The amphipathic high molecular compound (I) or (III) is useful as a highmolecular type surfactant and has made it possible to efficientlyproduce the water dispersible type resin composition (IV), that is, thewater dispersible particles having a heteromorphologic structure coveredwith a highly hydrophilic polymer, which have been insufficiently formedby conventional techniques, by emulsion-polymerizing a hydrophobicethylenically unsaturated compound in the presence of the compound (I)or (III).

The hydrophobic ethylenically unsaturated compound is mainly used forthe ethylenically unsaturated compound. However, a hydrophilicethylenically unsaturated compound which is usually used for the purposeof improving the stability of polymers may be added in thepolymerization. The amount thereof falls usually in a range of 0.1 to 20weight % based on the weight of the hydrophobic ethylenicallyunsaturated compound.

The amphipathic high molecular compound [C] used in the presentinvention is the amphipathic high molecular compound (I) or (III)described above. With respect to the composition ratio of compound [C]to the ethylenically unsaturated compound [D], the compound [C] of lessthan 1 weight % based on the total weight of the compounds [C] and [D]in terms of solids lowers the emulsification stability of the resincomposition of the present invention and therefore is not preferred.Accordingly, the ratio of [C] falls in a range of 1 to 99 weight % andthat of [D] in a range of 99 to 1 weight %, preferably that of [C] in arange of 5 to 90 weight % and that of [D] in a range of 95 to 10 weight%.

The water dispersible type resin composition (IV) of the presentinvention can be produced by known emulsion-polymerization methods inthe presence of a pH controller, a chain transfer agent, a protectivecolloid agent and a known surfactant, according to necessity. Thecompounds exemplified in the water dispersible type resin composition(II) can be used as the protective colloid agent. The use amount thereoffalls usually in a range of 0.1 to 20%, preferably 0.1 to 10% based onthe whole amount of the ethylenically unsaturated compounds.

A method for emulsion-polymerizing the ethylenically unsaturatedcompound is not specifically restricted, and the polymerization can becarried out by known methods. Usually, the polymerization is carried outby maintaining the polymerizing solution at prescribed temperatures inthe presence of a radical polymerization initiator. The temperature doesnot have to be maintained at the same temperature during thepolymerization and may suitably be changed as the polymerization goeson. The polymerization is carried out while heating or cooling, ifnecessary. The polymerization temperature is varied depending on thekinds of the ethylenically unsaturated compound and the polymerizationinitiators to be used. In the case of the single initiator, thepolymerization temperature falls usually in a range of 30 to 200° C. Onthe other hand, in the case of a redox polymerization initiator, thetemperature is lowered; when the redox polymerization is carried out inone lot, the temperature is usually -5 to 50° C.; and in the redoxpolymerization case where the components are added consecutively, thetemperature is usually 30 to 90° C. An atmosphere in a polymerizationvessel is not specifically restricted. For the purpose of carrying outrapidly the polymerization, the atmosphere is preferably substitutedwith inert gas such as nitrogen gas. The polymerization time is notspecifically limited and is usually 1 to 40 hours.

Water is used as a polymerization solvent, and organic solvents such asmethanol, ethanol, isopropanol, acetone, ethylene glycol, and propyleneglycol may be used in combination.

The high molecular surfactant, the ethylenically unsaturated compound,the polymerization initiator, the solvent, and the chain transfer agentwhich all are used for the polymerization may be charged into a reactionvessel in one lot at the time when the polymerization starts, or one ormore components may be added singly or in the form of a mixture thereofwith the solvent, for example, an emulsion solution into which theethylenically unsaturated compound is turned in the presence of the highmolecular surfactant, consecutively as the polymerization proceeds.

The water dispersible type resin composition produced in the presentinvention is basically of spherical particles and composed of ahydrophobic polymer in the inner part and a hydrophilic polymer in theouter part. The above resin composition is characterized in that thehydrophilic polymer free from the particles is scarcely present. Thehigh molecular surfactant of the present invention forms particles in adiluted aqueous solution, and the size thereof can be determined by adynamic light scattering method. It is supported by the fact that thediameter of particles contained in the emulsion prepared by polymerizingthe hydrophobic ethylenically unsaturated compound remains unchangeduntil the amount of the hydrophobic ethylenically unsaturated compoundreaches some fixed amount based on the high molecular surfactant, but asthe amount of the hydrophobic ethylenically unsaturated compound growsexceeding the above fixed amount, the diameter of the particlescontained in the emulsion increases, and the particles having a particlediameter observed in the case of the high molecular surfactant alonecease to be present.

The water dispersible type resin composition (IV) of the presentinvention may further contain, if necessary, additives such aspreservatives, defoaming agents, cross-linking agents, viscositycontrollers, film forming aids, plasticizers, antistatic agents,sticking agents, freezing stabilizers, pigments, fillers and dyes.

The water dispersible type resin composition (IV) of the presentinvention is used in the fields of plasticizers, heat resistant resins,antistatic agents, lubricants, paints, adhesives, additives for cement,and paper making additives.

The amphipathic high molecular compounds (I) and (III) and the waterdispersible type resin composition (IV) according to the presentinvention provide paper with a sizing property and enhance as well paperstrength to a large extent by coating them on the surface of paper. Theconcentration of a coating solution in coating on paper falls in a rangeof 0.01 to 10.0%, preferably 0.10 to 8.0%. The coated amount thereoffalls in a range of 0.001 to 5.0 g/m², preferably 0.005 to 1.0 g/m².Coating on paper is carried out by conventional methods such asimpregnation, size press, gate roll coater, calendering, blade coater,and spraying. The drying temperature after coating may be temperaturesat which water is evaporated and falls preferably in a range of from 80°C. to 180° C. Further, the amphipathic high molecular compounds (I) and(III) and the water dispersible type resin composition (IV) according tothe present invention can improve still more the surface strength andthe internal strength by combining with chemicals for surface coatingsuch as starch, carboxymethyl cellulose, PVA and PAM group which have sofar been known.

Further, the amphipathic high molecular compounds (I) and (III) and thewater dispersible type resin composition (IV) according to the presentinvention can be used in combination with pigments, other sizing agents(ASA group, AKD group, rosin group and synthetic high molecularcompounds), waterproofing agents, releasing agents, defoaming agents,and rust preventives. The examples of the pigments used includeinorganic pigments such as clay, light calcium carbonate, heavy calciumcarbonate, titanium oxide, aluminum hydroxide, satin white, bariumsulfate, magnesium oxide, talc, silica and colloidal silica, and organicpigments such as polystyrene, SBR and phenol resins. They can be usedsingly or in combination of two or more kinds thereof. They can be usedas well in combination with dispersants, viscosity controllers, waterretention aids, dyes, fluorescent dyes, solvents, pH controllers,surfactants and preservatives.

Further, the amphipathic high molecular compounds (I) and (III) and thewater dispersible type resin composition (IV) according to the presentinvention can be fixed on pulp by interaction with aluminum sulfate,aluminum chloride, sodium aluminate, Mannich Modifications and Hofmannmodifications of polyethylenimine and polyacrylamide,polyalkylenepolyamine, and water soluble polymer having a cation groupsuch as cationic starch, which are widely used as fixing agents forimproving the consumption efficiency of sizing agents. They can be usedas an internal sizing agent. When they are used as the internal sizingagent, the addition amount thereof is 0.01 to 4.0 weight %, preferably0.05 to 2.0 weight % based on the weight of pulp, and they are added atthe same place as conventional internal sizing agents such as a seed boxand a machine chest.

EXAMPLES

The present invention will be explained below in detail with referenceto examples but the present invention shall not be restricted to theseexamples. In the following examples, percentage is based on weight, andviscosity is a value measured with a B type viscometer at 25° C.Molecular weight was determined by GPC analysis, wherein Shodex OH-pakSB-80M+SB-804 (manufactured by Showa Denko Co., Ltd.) was used as acolumn, and Na₂ HPO₄ --KH₂ HPO₄ (50 mM) --NaNO₃ (0.1 M) (pH 6.5) wasused for the eluent. NMR analysis was carried out with an NMR spectrummeasuring apparatus A500 of 500 MHz (manufactured by JEOL Ltd.), whereina sample was dissolved homogeneously in deuterated chloroform in aconcentration of about 10 to 20% w/v, and the solution was put in an NMRspectrum measuring sample tube having an outer diameter of 5 mm todetermine a ¹ H- and ¹³ C-NMR spectrum. IR analysis was carried out withan infrared analytical apparatus FT/IR-8900 (JAPAN SPECTROSCOPIC Co.,Ltd.) using an aperture plate of MS-5 or KBr tablet. Elemental analysiswas carried out with a CHN analytical apparatus model 2400 (manufacturedby Perkin-Elmer Co., Ltd.).

In the symbols put in front of the abbreviations of the compounds, L-represents ASA of an α-olefin type; B-represents ASA of an internalolefin type; and C_(n) represents a carbon number.

B-C₁₆ -ESA-MA Example 1

A four neck separable flask of 1 l equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with B-C₁₆-ESA (C₁₆ type, Colopearl Z-100 manufactured by Seiko ChemicalIndustries Co., Ltd.) of 645.0 g, and allylamine of 114.2 g was addeddropwise thereto through the dropping funnel in 90 minutes whilestirring. The reaction temperature was controlled to 32 to 42° C. by awater bath during dropping, and stirring was further continued at 40° C.for 3 hours after dropping was finished, whereby an amber highly viscousliquid of 759.2 g was obtained. While B-C₁₆ -ESA had a viscosity of 96cp before the reaction, the reaction product (B-C₁₆ -ESA-MA) had aviscosity of 52,300 cp.

Elemental analysis value (C₂₃ H₄₁ NO₃); Calculated value: C: 72.78%, H:10.89%, N: 3.69%; Measured value : C: 73.42%, H: 11.12%, N: 3.41%.

IR analysis (FIG. 1) was carried out to find that the characteristicabsorption bands (C═O stretching) of the acid anhydride group in the rawmaterial B-C₁₆ -ESA observed in 1780 cm⁻¹ and 1860 cm⁻¹ disappeared andthat instead of them, there were observed an absorption band originatingin carboxylic acid (C═O stretching) in 1700 cm⁻¹, and absorption bandsoriginating in amide (C═O stretching and N--H deforming) in 1640 cm⁻¹and 3300 cm⁻¹ (N--H stretching).

A ¹ H-NMR spectrum and a ¹³ C-NMR spectrum of B-C₁₆ -ESA-MA were shownin FIG. 2 and FIG. 3. The strength of a magnetic field in the axis ofabscissas is shown by ppm unit on the basis (0 ppm) oftetramethylsilane. Used for the assignment of these NMR signals werevarious NMR determining methods such as DEPT (Distortionless Enhancementby Polarization Transfer), ¹ H-COSY (Correlation Spectroscopy), and C-Hcorrelation COSY. In particular, carbonyl carbons were assigned byanalyzing the ¹³ C-NMR spectrum of B-C₁₆ -ESA-MA in which the carboxylgroup was esterified to methyl ester by diazomethane and a C-Hcorrelation COSY spectrum of a long range.

As a result thereof, it was found that the signals seen in 172.3 and172.6 ppm corresponded to the carbonyl carbon of an amide group of anisomer having the structure represented by Formula (2) out of twoposition isomers of B-C₁₆ -ESA-MA and that the signals seen in 178.2 and178.8 ppm corresponded to the carbonyl carbon of a carboxyl group of thesame isomer. On the other hand, the signals seen in 174.5 and 174.9 ppmcorresponded to the carbonyl carbon of an amide group of an isomerhaving the structure represented by Formula (1), and the signals seen in176.6 and 177.0 ppm corresponded to the carbonyl carbon of a carboxylgroup of the same isomer. Each two signals are observed in therespective carbonyl carbons, and this is considered due to the fact thattwo kinds of diastereoisomers are present since B-C₁₆ -ESA-MA has twoasymmetric carbons adjacent to each other in the molecule.

¹ H-NMR (CDCl3): δ 0.88 (t, 6H, CH₃ of R₁ and R₂); 1.26 (m, 20H, CH₂ ofR₁ and R₂); 1.99 (m, 2H, C*HCH═CHCH₂ CH₂); 2.25 (m, 1H, C*HCH═CH),2.28-2.71 (dd, 2H, COC*HCH₂ CO); 2.70 & 2.89 (m, 1H, COC*HCH₂ CO); 3.83(m, 2H, NHCH₂ CH═CH₂); 4.97-5.25 (m, 1H, C*HCH═CH); 5.09-5.19 (m, 2H,NHCH₂ CH═CH₂); 5.40 (m, 1H, C*HCH═CH), 5.75-5.83 (m, 1H, NHCH₂ CH═CH₂);6.21-6.40 (m, 1H, NHCH₂ CH═CH₂); 9.52 (brs, 1H, COOH).

¹³ C-NMR (CDCl₃): δ 14.1 (q, 2CH₃); 22.7 (t, CH₃ CH₂ CH₂); 29.1-29.8 (m,CH₂ of R₁ and R₂); 31.9 (t, CH₃ CH₂ CH₂); 32.6 (t, C*HCH═CHCH₂); 36.1(t, COC*HCH₂ CO); 42.1 (t, NHCH₂ CH═CH₂); 44.9 (d, C*HCH═CH); 46.7 &47.5 (d, COC*HCH₂ CO); 116.4 (t, NHCH₂ CH═CH₂); 130.2-130.8 (d,C*HCH═CH); 133.2-133.7 (d, C*HCH═CH); 133.9-134.2 (d, NHCH₂ CH═CH₂);172.3 & 172.6 (s, COC*HCH₂ CONH); 174.5 & 174.9 (s, COCH₂ C*HCONH);176.6 & 177.0 (s, COCH₂ C*HCONH); 178.2 & 178.8 (s, COC*HCH₂ CONH).Provided that C* represents an asymmetrical carbon.

B-C₁₆ -ESA-MA obtained above was dissolved in water in the form of acarboxylic acid salt, and an aqueous solution (pH 8.96) prepared bydissolving homogeneously B-C₁₆ -ESA-MA of 40.0 g, a 40% sodium hydroxideaqueous solution of 10.5 g, and distilled water of 349.5 g was used inthe following examples.

B-C₁₆ -ESA-DA Example 2

A four neck separable flask of 1 l equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with B-C₁₆-ESA (C₁₆ type, Colopearl Z-100 manufactured By Seiko ChemicalIndustries Co., Ltd.) of 645.0 g, and diallylamine of 194.3 g was addeddropwise thereto through the dropping funnel in 40 minutes whilestirring. The reaction temperature was controlled to 20 to 30° C. by awater bath during dropping, and stirring was further continued at 30° C.for 3 hours after dropping was finished, whereby an amber highly viscousliquid of 839.3 g was obtained. B-C₁₆ -ESA-DA had a viscosity of 1,980cp.

Elemental analysis value (C₂₆ H₄₅ NO₃); Calculated value: C: 74.41%, H:10.81%, N: 3.34%; Measured value: C: 74.42%, H: 11.10%, N: 3.10%.

In IR analysis (FIG. 4), there were observed an absorption bandoriginating in carboxylic acid (C═O stretching) in 1720 cm⁻¹, and anabsorption band originating in amide (C═O stretching) in 1650 cm⁻¹.

A ¹ H-NMR spectrum and a ¹³ C-NMR spectrum of B-C₁₆ -ESA-DA were shownin FIGS. 5a and 5b and FIGS. 6a and 6b. As can be found from a carbonylcarbon range in the ¹³ C-NMR spectrum, an amide group and a carboxylgroup contained in the isomer having the structure represented byFormula (1) show very small signal strengths (175.0 & 175.2 ppm and177.4 & 177.6 ppm) originating in the carbonyl carbons thereof. Thisreveals that the isomer having the structure represented by Formula (2)out of two kinds of position isomers occupy the most part in B-C₁₆-ESA-DA.

¹ H-NMR (CDCl3): δ 0.88 (t, 6H, CH₃ of R₁ and R₂); 1.26 (m, 20H, CH₂ ofR₁ and R₂); 1.98 (m, 2H, C*HCH═CHCH₂ CH₂); 2.24 (m, 1H, C*HCH═CH),2.29-2.78 (dd, 2H, COC*HCH₂ CO); 2.75 & 2.99 (m, 1H, COC*HCH₂ CO);3.78-4.02 (m, 4H, 2NCH₂ CH═CH₂); 5.04-5.28 (m, 1H, C*HCH═CH); 5.09-5.20(m, 4H, 2NCH₂ CH═CH₂); 5.36-5.43 (m, 1H, C*HCH═CH), 5.74 (m, 2H, 2NCH₂CH═CH₂); 10.90 (s, 1H, COOH).

¹³ C-NMR (CDCl₃): δ 14.1 (q, 2CH₃); 22.7 (t, CH₃ CH₂ CH₂); 29.2-29.8 (m,CH₂ of R₁ and R₂); 31.9 (t, CH₃ CH₂ CH₂); 32.6 (t, C*HCH═CHCH₂); 32.8(t, COC*HCH₂ CO); 45.1 (d, C*HCH═CH); 46.5 & 47.3 (d, COC*HCH₂ CO); 48.1& 49.4 (t, 2NCH₂ CH═CH₂); 116.8-117.2 (t, 2NCH₂ CH═CH₂); 131.0-131.5 (d,C*HCH═CH); 132.6-133.0 (d, C*HCH═CH); 132.8-133.3 (d, 2NCH₂ CH═CH₂);172.2 & 172.5 (s, COC*HCH₂ CON); 175.0 & 175.2 (s, COCH₂ C*HCON); 177.4& 177.6 (s, COCH₂ C*HCON); 178.5 & 179.2 (s, COC*HCH₂ CON). Providedthat C* represents an asymmetrical carbon.

B-C₁₆ -ESA-DA obtained above was dissolved in water in the form of acarboxylic acid salt, and an aqueous solution (pH 9.02) prepared bydissolving homogeneously B-C₁₆ -ESA-DA of 40.0 g, a 40% sodium hydroxideaqueous solution of 9.5 g, and distilled water of 350.5 g was used inthe following examples.

B-C₁₈ -ESA-MA Example 3

A four neck separable flask of 2 l equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with B-C₁₈-ESA (C₁₈ type, Pabelas NP manufactured By Mitsubishi Oil Co., Ltd.) of1402.2 g, and allylamine of 228.4 g was added dropwise thereto throughthe dropping funnel in 40 minutes while stirring. The reactiontemperature was controlled to 20° C. at the beginning of dropping and55° C. at the end of dropping by a water bath, and stirring was furthercontinued at 40° C. for one hour after dropping was finished, whereby areddish brown highly viscous liquid of 1,630.6 g was obtained. WhileB-C₁₈ -ESA had a viscosity of 185 cp before the reaction, the reactionproduct (B-C₁₈ -ESA-MA) had a viscosity of 83,900 cp.

Elemental analysis value (C₂₅ H₄₅ NO₃); Calculated value: C: 73.66%, H:11.13%, N: 3.44%; Measured value : C: 73.88%, H: 11.53%, N: 4.03%.

IR analysis revealed that the characteristic absorption bands (C═Ostretching) of the acid anhydride groups in the raw material B-C₁₈ -ESAobserved in 1780 cm⁻¹ and 1860 cm⁻¹ disappeared, and instead of them,there were observed an absorption band originating in carboxylic acid(C═O stretching) in 1700 cm⁻¹, and absorption bands originating in amide(C═O stretching and N--H deforming) in 1640 cm⁻¹ and 3300 cm⁻¹ (N--Hstretching).

The structure of B-C₁₈ -ESA-MA was confirmed by measuring a ¹ H-NMRspectrum and a ¹³ C-NMR spectrum.

B-C₁₈ -ESA-MA obtained above was dissolved in water in the form of acarboxylic acid salt, and a 80 weight % aqueous solution (pH 8.97,viscosity 3520 cp) prepared by adding a 40% sodium hydroxide aqueoussolution of 186.2 g and distilled water of 54.7 g to B-C₁₈ -ESA-MA of759.1 g and dissolving them homogeneously was used in the followingexamples.

L-C₈ ESA-MA Example 4

A four neck separable flask of 100 ml equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with L-C₈-ESA (C₈ type, 2-octenylsuccinic anhydride manufactured By Tokyo KaseiKogyo Co., Ltd.) of 25.1 g, and allylamine of 6.8 g was added dropwisethereto through the dropping funnel in 10 minutes while stirring. Thereaction temperature was controlled to 30° C. by a water bath, andstirring was further continued at 30° C. for 5.5 hours after droppingwas finished, whereby a pale yellow highly viscous liquid was obtained.The liquid was solidified by leaving for standing at room temperaturesafter the reaction.

Elemental analysis value (C₁₅ H₂₅ NO₃); Calculated value: C: 67.38%, H:9.42%, N: 5.24%; Measured value : C: 67.47%, H: 9.42%, N: 5.66%.

The structure of L-C₈ -ESA-MA was confirmed by measuring an IR spectrum,a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

L-C₁₀ -ESA-MA Example 5

L-C₁₀ -ESA-MA was obtained by reacting equimolar allylamine in the samemanner as in Example 4, except that L-C₁₀ -ESA (C₁₀ type,2-decenylsuccinic anhydride manufactured By Tokyo Kasei Kogyo Co., Ltd.)was used.

Elemental analysis value (C₁₇ H₂₉ NO₃); Calculated value: C: 69.12%, H:9.89%, N: 4.74%; Measured value : C: 68.85%, H: 10.34%, N: 4.28%.

The structure of L-C₁₀ -ESA-MA was confirmed by measuring an IRspectrum, a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

L-₁₂ -ESA-MA Example 6

A four neck separable flask of 100 ml equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with L-C₁₂-ESA (C₁₂ type, 2-dodecenylsuccinic anhydride manufactured By TokyoKasei Kogyo Co., Ltd.) of 25.0 g, and acetone of 50 ml was added todissolve it, followed by adding dropwise thereto allylamine of 5.4 gthrough the dropping funnel in 10 minutes while stirring. The reactiontemperature was controlled to 25° C. by a water bath, and stirring wasfurther continued at 25° C. for 5.5 hours after dropping was finished.

After distilling acetone off with an evaporator, the residue wasrecrystallized from acetone to obtain a white solid.

Elemental analysis value (C₁₉ H₃₃ NO₃); Calculated value: C: 70.55%, H:10.28%, N: 4.33%; Measured value : C: 71.48%, H: 10.88%, N: 4.47%.

The structure of L-C₁₂ -ESA-MA was confirmed by measuring an IRspectrum, a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

Examples 7 to 9

L-C₁₄ -ESA-MA, L-C₁₆ -ESA-MA and L-C₁₈ -ESA-MA were obtained by reactingequimolar allylamine in the same manner as in Example 6, except that2-tetradecenylsuccinic anhydride, 2-hexadecenylsuccinic anhydride and2-octadecenylsuccinic anhydride were used, respectively.

L-C₁₄ -ESA-MA (Example 7)

Elemental analysis value (C₂₁ H₃₇ NO₃); Calculated value: C: 71.75%, H:10.61%, N: 3.98%; Measured value : C: 72.21%, H: 11.28%, N: 4.12%.

L-C₁₆ -ESA-MA (Example 8)

Elemental analysis value (C₂₃ H₄₁ NO₃); Calculated value: C: 72.78%, H:10.89%, N: 3.69%; Measured value : C: 73.33%, H: 11.52%, N: 3.67%.

L-C₁₈ -ESA-MA (Example 9)

Elemental analysis value (C₂₅ H₄₅ NO₃); Calculated value: C: 73.66%, H:11.13%, N: 3.44%; Measured value : C: 73.95%, H: 11.78%, N: 3.52%.

The structures of the three compounds described above were confirmed bymeasuring IR spectra, ¹ H-NMR spectra and ¹³ C-NMR spectra.

L-C₁₂ -PSA-MA Example 10

A four neck separable flask of 1 l equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with L-C₁₂-PSA (C₁₂ type, MSP manufactured By Mitsubishi Oil Co., Ltd.) of 266.4g, and allylamine of 57.1 g was added dropwise thereto through thedropping funnel in 30 minutes while stirring. The reaction temperaturewas controlled to 40° C. by a water bath during dropping, and stirringwas further continued at 50° C. for 5 hours after dropping finished,whereby a dark brown highly viscous liquid of 323.5 g was obtained.

Elemental analysis value (C₁₉ H₃₃ NO₃); Calculated value: C: 70.55%, H:10.28%, N: 4.33%; Measured value : C: 70.01%, H: 9.97%, N: 4.43%.

IR analysis revealed that the characteristic absorption bands (C═Ostretching) of the acid anhydride groups in the raw material PSAobserved in 1780 cm⁻¹ and 1860 cm⁻¹ disappeared and that instead ofthem, there were observed an absorption band originating in carboxylicacid (C═O stretching) in 1710 cm⁻¹, and absorption bands originating inamide (C═O stretching and N--H deforming) in 1640 cm⁻¹ and 3300 cm⁻¹(N--H stretching).

The structure of L-C₁₂ -PSA-MA was confirmed by measuring a ¹ H-NMRspectrum and a ¹³ C-NMR spectrum.

L-C₁₂ -PSA-MA obtained above was dissolved in water in the form of acarboxylic acid salt, and an aqueous solution (pH 8.99) prepared byadding a 40% sodium hydroxide aqueous solution of 12.4 g and distilledwater of 347.6 g to L-C₁₂ -PSA-MA of 40.0 g and dissolving themhomogeneously was used in the following examples.

L-C₁₂ -PSA-DA Example 11

A four neck separable flask of 1 l equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with L-C₁₂-PSA (C₁₂ type, MSP manufactured By Mitsubishi Oil Co., Ltd.) of 266.4g, and diallylamine of 97.2 g was added dropwise thereto through thedropping funnel in 15 minutes while stirring. The reaction temperaturewas controlled to 40° C. by a water bath during dropping, and stirringwas further continued at 40° C. for 4 hours after dropping was finished,whereby a dark brown highly viscous liquid of 363.6 g was obtained.

Elemental analysis value (C₂₂ H₃₇ NO₃); Calculated value: C: 72.69%, H:10.26%, N: 3.85%; Measured value: C: 72.29%, H: 10.30%, N: 4.04%.

Observed by IR analysis were an absorption band originating incarboxylic acid (C═O stretching) in 1720 cm⁻¹ and an absorption bandoriginating in amide (C═O stretching) in 1650 cm⁻¹.

The structure of L-C₁₂ -PSA-DA was confirmed by measuring a ¹ H-NMRspectrum and a ¹³ C-NMR spectrum.

L-C₁₂ -PSA-DA obtained above was dissolved in water in the form of acarboxylic acid salt, and an aqueous solution (pH 8.43) prepared byadding a 40% sodium hydroxide aqueous solution of 11.0 g and distilledwater of 349.0 g to L-C₁₂ -PSA-DA of 40.0 g and dissolving themhomogeneously was used in the following examples.

L-C₂₄ -BSA-MA Example 12

A four neck separable flask of 1 l equipped with a stirrer, a ref luxcondenser, a thermometer and a dropping funnel was charged with L-C₂₄-BSA (C₂₄ type, LV-7M manufactured By Nippon Petrochemicals Co., Ltd.)of 200.0 g, and acetone of 470.0 g was added to dissolve it, followed byadding dropwise thereto allylamine of 25.4 g through the dropping funnelin 30 minutes while stirring at 20° C. Stirring was continued at 20° C.for one hour after dropping finished and further for 2 hours afterelevating the temperature to 40° C. The solvent contained in thereaction liquid was distilled off under reduced pressure, whereby a darkbrown highly viscous liquid of 225.4 g was obtained.

Elemental analysis value (C₃₁ H₅₇ NO₃); Calculated value: C: 75.71%, H:11.68 %, N: 2.85%; Measured value: C: 75.99%, H: 11.58%, N: 2.89%.

IR analysis revealed that the characteristic absorption bands (C═Ostretching) of an acid anhydride group in the raw material L-C₂₄ -BSAobserved in 1780 cm⁻¹ and 1860 cm⁻¹ disappeared and that instead ofthem, there were observed an absorption band originating in carboxylicacid (C═O stretching) in 1705 cm⁻¹, and absorption bands originating inamide (C═O stretching and N--H deforming) in 1640 cm⁻¹ and 3300 cm⁻¹(N--H stretching).

The structure of L-C₂₄ -BSA-MA was confirmed by measuring a ¹ H-NMRspectrum and a ¹³ C-NMR spectrum.

L-C₂₄ -BSA-MA obtained above was dissolved in water in the form of acarboxylic acid salt, and an aqueous solution (pH 8.97) prepared byadding a 40% sodium hydroxide aqueous solution of 8.6 g and distilledwater of 351.4 g to L-C₂₄ -BSA-MA of 40.0 g and dissolving themhomogeneously was used in the following examples.

L-C₂₄ -BSA-DA Example 13

A four neck separable flask of 1 l equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with L-C₂₄-BSA (C₂₄ type, LV-7M manufactured By Nippon Petrochemicals Co., Ltd.)of 200.0 g, and acetone of 470.0 g was added to dissolve it, followed byadding dropwise thereto diallylamine of 43.3 g through the droppingfunnel in 37 minutes while stirring at 20° C. Stirring was continued at20° C. for one hour after dropping finished and further for 2 hoursafter elevating the temperature to 40° C. The solvent contained in thereaction liquid was distilled off under reduced pressure, whereby a darkbrown highly viscous liquid of 242.5 g was obtained.

Elemental analysis value (C₃₄ H₆₁ NO₃); Calculated value: C: 76.78%, H:11.56%, N: 2.63%; Measured value : C: 77.29%, H: 12.05%, N: 2.80%.

Observed by IR analysis were an absorption band originating incarboxylic acid (C═O stretching) in 1710 cm⁻¹ and an absorption bandoriginating in amide (C═O stretching) in 1650 cm⁻¹.

The structure of L-C₂₄ -BSA-DA was confirmed by measuring a ¹ H-NMRspectrum and a ¹³ C-NMR spectrum.

L-C₂₄ -BSA-DA obtained above was dissolved in water in the form of acarboxylic acid salt, and an aqueous solution (pH 8.99) prepared byadding a 40% sodium hydroxide aqueous solution of 7.9 g and distilledwater of 352.1 g to L-C₂₄ -BSA-DA of 40.0 g and dissolving themhomogeneously was used in the following examples.

B-C₁₆ -ESA-AL Reference Example 1

A four neck separable flask of 300 ml equipped with a stirrer, a ref luxcondenser, a thermometer and a dropping funnel was charged with B-C₁₆-ESA (C₁₆ type, Colopearl Z-100 manufactured By Seiko ChemicalIndustries Co., Ltd.) of 100.0 g, and a mixed solution of allyl alcoholof 18.0 g and sulfuric acid of 0.31 g was added dropwise thereto throughthe dropping funnel in 30 minutes while stirring. The reactiontemperature was controlled to 40° C. by a water bath during dropping,and stirring was further continued at 40° C. for 3 hours after droppingwas finished, whereby an amber viscous liquid of 118.3 g was obtained.While B-C₆ -ESA had a viscosity of 96 cp before the reaction, thereaction product (B-C₁₆ -ESA-AL) had a viscosity of 197 cp.

Elemental analysis value (C₂₃ H₄₀ O₄); Calculated value: C: 72.59%, H:10.59%; Measured value: C: 72.26%, H: 10.97%.

IR analysis (FIG. 7) was carried out to find that the characteristicabsorption bands (C═O stretching) of the acid anhydride groups in theraw material B-C₁₆ -ESA observed in 1780 cm⁻¹ and 1860 cm⁻¹ disappearedand that instead of them, there were observed an absorption bandoriginating in carboxylic acid (C═O stretching) in 1700 cm⁻¹ and anabsorption band originating in ester (C═O stretching) in 1740 cm⁻¹.

A ¹ H-NMR spectrum and a ¹³ C-NMR spectrum of B-C₁₆ -ESA-AL were shownin FIG. 8 and FIG. 9. The strength of a magnetic field in the axis ofabscissas is shown by ppm unit on the basis (0 ppm) oftetramethylsilane. Used for the assignment of these NMR signals werevarious NMR determining methods such as DEPT (Distortionless Enhancementby Polarization Transfer), ¹ H-COSY (Correlation Spectroscopy), and C-Hcorrelation COSY.

¹ H-NMR (CDCl₁₃): δ 0.88 (t, 6H, CH₃ of R₁ and R₂); 1.26 (m, 20H, CH₂ ofR₁ and R₂); 1.99 (m, 2H, C*HCH═CHCH₂ CH₂); 2.25 & 2.32 (m, 1H,C*HCH═CH), 2.40-2.78 (dd, 2H, COC*HCH₂ CO); 2.83 & 2.94 (m, 1H, COC*HCH₂CO); 4.57 (t, 2H, OCH₂ CH═CH₂); 5.04-5.19 (m, 1H, C*HCH═CH); 5.21-5.32(m, 2H, OCH₂ CH═CH₂); 5.44 (m, 1H, C*HCH═CH), 5.85-5.93 (m, 1H, OCH₂CH═CH₂); 11.27 (s, 1H, COOH).

¹³ C-NMR (CDCl₃): δ 14.1 (q, 2CH₃); 22.7 (t, CH₃ CH₂ CH₂); 29.1-29.7 (m,CH₂ of R₁ and R₂); 32.0 (t, CH₃ CH₂ CH₂); 32.6 (t, C*HCH═CHCH₂);33.2-33.8 (t, COC*HCH₂ CO); 44.6 & 44.8 (d, C*HCH═CH); 45.7 & 46.0 (d,COC*HCH₂ CO); 65.4 (t, OCH₂ CH═CH₂); 118.3 (t, OCH₂ CH═CH₂); 129.6 (d,C*HCH═CH); 132.0 (d, OCH₂ CH═CH₂); 133.7 & 134.1 (d, C*HCH═CH); 171.9 &172.0 (s, COC*HCH₂ CO); 180.1 & 180.7 (s, COC*HCH₂ CO). Provided that C*represents an asymmetrical carbon.

B-C₁₆ -ESA-AL obtained above was dissolved in water in the form of acarboxylic acid salt, and an aqueous solution (pH 9.13) prepared bydissolving homogeneously B-C₁₆ -ESA-AL of 40.0 g, a 40% sodium hydroxideaqueous solution of 11.4 g, and distilled water of 348.6 g was used inthe following examples.

B-C₁₈ -ESA-AL Reference Example 2

A four neck separable flask of 1 l equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with B-C₁₈-ESA (C₁₈ type, Pabelas NP manufactured By Mitsubishi Oil Co., Ltd.) of500.0 g, and a mixed solution of allyl alcohol of 82.8 g and sulfuricacid of 1.84 g was added dropwise thereto through the dropping funnel in15 minutes while stirring. The reaction temperature was controlled to40° C. by a water bath during dropping, and stirring was furthercontinued at 40° C. for 5 hours after dropping was finished, whereby areddish brown, transparent viscous liquid was obtained. While B-C₁₈ -ESAhad a viscosity of 185 cp before the reaction, the reaction product(B-C₁₈ -ESA-AL) had a viscosity of 275 cp.

Elemental analysis value (C₂₅ H₄₄ O₄); Calculated value: C: 73.48%, H:10.85%; Measured value: C: 72.72%, H: 11.12%;

The structure of B-C₁₈ -ESA-AL was confirmed by measuring an IRspectrum, a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

B-C₁₈ -ESA-AL obtained above was dissolved in water in the form of acarboxylic acid salt, and an aqueous solution (pH 9.13) prepared bydissolving homogeneously B-C₁₈ -ESA-AL of 40.0 g, a 40% sodium hydroxideaqueous solution of 12.2 g and distilled water of 347.8 g was used inthe following examples.

L-C₁₂ -PSA-AL Reference Example 3

A four neck separable flask of 300 ml equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with L-C₁₂-PSA (C₁₂ type, MSP manufactured By Mitsubishi Oil Co., Ltd.) of 100.0g, and a mixed solution of allyl alcohol of 21.8 g and sulfuric acid of0.37 g was added dropwise thereto through the dropping funnel in 30minutes while stirring. The reaction temperature was controlled to 40°C. by a water bath during dropping, and stirring was further continuedat 40° C. for 3 hours after dropping was finished, whereby an amberhighly viscous liquid of 122.1 g was obtained. While L-C₁₂ -PSA had aviscosity of 370 cp before the reaction, the reaction product (L-C₁₂-PSA-AL) had a viscosity of 1,020 cp.

Elemental analysis value (C₁₉ H₃₂ O₄); Calculated value: C: 70.33 %, H:9.94%; Measured value: C: 69.95%, H: 10.31%.

The structure of L-C₁₂ -PSA-AL was confirmed by measuring an IRspectrum, a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

L-C₁₂ -PSA-AL obtained above was dissolved in water in the form of acarboxylic acid salt, and an aqueous solution (pH 8.22) prepared bydissolving homogeneously L-C₁₂ -PSA-AL of 40.0 g, a 40 % sodiumhydroxide aqueous solution of 12.4 g and distilled water of 347.6-g wasused in the following examples.

L-C₂₄ -BSA-AL Reference Example 4

A four neck separable flask of 300 ml equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with L-C₂₄-BSA (C₂₄ type, LV-7M manufactured By Nippon Petrochemicals Co., Ltd.)of 100.0 g, and a mixed solution of allyl alcohol of 12.9 g and sulfuricacid of 0.22 g was added dropwise thereto through the dropping funnel in30 minutes while stirring. The reaction temperature was controlled to40° C. by a water bath during dropping, and stirring was furthercontinued at 40° C. for 4 hours after dropping was finished, whereby anamber highly viscous liquid of 113.1 g was obtained. While L-C₂₄ -BSAhad a viscosity of 4,020 cp before the reaction, the reaction product(L-C₂₄ -BSA-AL) had a viscosity of 3,070 cp.

Elemental analysis value (C₃₁ H₅₆ O₄); Calculated value: C: 75.56%, H:11.45%; Measured value: C: 75.47%, H: 12.12%.

The structure of L-C₂₄ -BSA-AL was confirmed by measuring an IRspectrum, a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

A yellow cloudy aqueous solution (pH 8.73) prepared by mixing L-C₂₄-BSA-AL of 40.0 g, a 40 % sodium hydroxide aqueous solution of 7.9 gand-distilled water of 352.1 g with stirring was used in the followingexamples.

B-C₁₆ -ESA-HM Example 14

A four neck separable flask of 300 ml equipped with a stirrer, a refluxcondenser, a thermometer and a dropping funnel was charged with B-C₁₆-ESA (C₁₆ type, Colopearl Z-100 manufactured By Seiko ChemicalIndustries Co., Ltd.) of 100.0 g and sulfuric acid of 0.37 g, and amixed solution of 2-hydroxyethyl methacrylate (hereinafter abbreviatedas HM) of 40.4 g and hydroquinone monomethyl ether of 0.2 g was addeddropwise thereto through the dropping funnel in 30 minutes whilestirring. The reaction temperature was controlled to 40° C. by a waterbath during dropping, and stirring was further continued at 40° C. for 8hours after dropping was finished, followed by adding triethylamine of0.73 g to neutralize sulfuric acid, whereby an amber highly viscousliquid of 141.7 g was obtained. While B-C₁₆ -ESA had a viscosity of 96cp before the reaction, the reaction product (B-C₁₆ -ESA-HM) had aviscosity of 552 cp.

Elemental analysis value (C₂₆ H₄₄ O₆); Calculated value: C: 68.99%, H:9.80%; Measured value: C: 68.65%, H: 10.02%.

IR analysis (FIG. 10) was carried out to find that the characteristicabsorption bands (C═O stretching) of an acid anhydride group in the rawmaterial B-C₁₆ -ESA observed in 1780 cm⁻¹ and 1860 cm³¹ 1 disappearedand that instead of them, there were observed an absorption bandoriginating in carboxylic acid (C═O stretching) in 1710 cm⁻¹ and anabsorption band originating in ester (C═O stretching) in 1740 cm⁻¹.

A ¹ H-NMR spectrum and a ¹³ C-NMR spectrum of B-C₁₆ -ESA-HM were shownin FIG. 11 and FIG. 12. The strength of a magnetic field in the axis ofabscissas is shown by ppm unit on the basis (0 ppm) oftetramethylsilane.

An aqueous solution (pH 10.62) prepared by dissolving homogeneouslyB-C₁₆ -ESA-HM of 20.0 g, a 40% sodium hydroxide aqueous solution of 4.4g and distilled water of 175.6 g was used in the following examples.

B-C₁₈ -ESA-AL-EOA (20) Example 15

A stainless steel autoclave having a volume of 150 ml was charged withB-C₁₈ -ESA-AL of 35.0 g (0.086 mole) and potassium hydroxide of 0.56 gas a catalyst and substituted with nitrogen after deaeration underreduced pressure. Then, the reactor was heated, and after thetemperature reached 100° C., the pressure was reduced to 50 Torr tocarry out dehydration. After finishing the dehydration, nitrogen wasintroduced into the reactor to an atmospheric pressure, and then EO of75 g (1.70 mole) was fed into the reactor at a feed rate of 16.2 g/hourto carry out the reaction. During the reaction, the reaction temperaturewas maintained at 100 to 115° C., and the reaction pressure wasmaintained at 4.0 to 6.0 kg/cm². After finishing the reaction, thereaction solution was ripened at 115° C. for one hour. Then, the innertemperature was lowered to 70° C., and acetic acid of 0.59 ml was addedas a neutralizing agent, whereby ethoxylate to which EO of 20 moles wasadded (hereinafter abbreviated as B-C₁₈ -ESA-AL-EOA (20)) of 110.0 g wasobtained.

Elemental analysis value (C₆₅ H₁₂₄ O₂₄); Calculated value: C: 60.54%, H:9.69%; Measured value: C: 60.44%, H: 9.67%.

The structure of B-C₁₈ -ESA-AL-EOA (20) was confirmed by measuring an IRspectrum, a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

B-C₁₈ -ESA-AL-EOA (15) Example 16

The reaction was carried out in the same manner as in Example 15, exceptthat there were changed the charge amount of potassium hydroxide to 0.48g and the feed amount of EO to 57 g (1.30 mole) (a feed rate of 21.3g/hour) and that the reaction was carried out at reaction temperaturesof 100 to 120° C. Further, acetic acid of 0.51 ml was added as aneutralizing agent, whereby ethoxylate to which EO of 15 moles was added(hereinafter abbreviated as B-C₁₈ -ESA-AL-EOA (15)) of 92.0 g wasobtained.

Elemental analysis value (C₅ H₁₀₄ O₉); Calculated value: C: 61.77%, H:9.80%; Measured value: C: 59.91%, H: 9.53%.

The structure of B-C₁₈ -ESA-AL-EOA (15) was confirmed by measuring an IRspectrum, a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

B-C₁₈ -ESA-AL-EOA (10) Example 17

The reaction was carried out in the same manner as in Example 15, exceptthat there were changed the charge amount of potassium hydroxide to 0.26g and the feed amount of EO to 38 g (0.86 mole) (a feed rate of 15.4g/hour) and that the reaction was carried out at reaction temperaturesof 100 to 120° C. Further, acetic acid of 0.41 ml was added as aneutralizing agent, whereby ethoxylate to which EO of 10 moles was added(hereinafter abbreviated as B-C₁₈ -ESA-AL-EOA (10)) of 73.0 g wasobtained.

Elemental analysis value (C₄₅ H₈₄ O₁₄); Calculated value: C: 63.65 %, H:9.97%; Measured value: C: 62.67%, H: 9.73%.

The structure of B-C₁₈ -ESA-AL-EOA (10) was confirmed by measuring an IRspectrum, a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

B-C₁₈ -ESA-AL-EOA (5) Example 18

The reaction was carried out in the same manner as in Example 15, exceptthat there were changed the charge amount of potassium hydroxide to 0.13g and the feed amount of EO to 20 g (0.45 mole) (a feed rate of 3.2g/hour) and that the reaction was carried out at reaction temperaturesof 100 to 120° C. Neutralization was not carried out, whereby ethoxylateto which EO of 5 moles was added (hereinafter abbreviated as B-C₁₈-ESA-AL-EOA (5)) of 55.0 g was obtained.

Elemental analysis value (C₃₅ H₆₄ O₉); Calculated value: C: 66.85%, H:10.26%; Measured value: C: 67.30%, H: 10.23%.

The structure of B-C₁₈ -ESA-AL-EOA (5) was confirmed by measuring an IRspectrum, a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

Example 19

The results of measuring the solubilities and the cloud points of B-C₁₈-ESA-AL-EOA (5), (10), (15) and (20) are summarized in Table 1.

                  TABLE 1                                                         ______________________________________                                                     Water solubility                                                              pH 5           pH 9    Cloud                                       or less pH 6 to 8 or more point (°C.)                                ______________________________________                                        B-C.sub.18 -ESA-AL                                                                           X       X        ⊚                                                                    --                                        B--C.sub.18 -ESA-AL-EOA (5) Δ Δ Δ  --.sup.1)                B--C.sub.18 -ESA-AL-EOA (10) Δ Δ Δ  --.sup.1)                                                    B--C.sub.18 -ESA-AL-EOA (15)                                                 ⊚ ⊚                                             ⊚ 34                       B--C.sub.18 -ESA-AL-EOA (20) ⊚ ⊚ .circlein                                          circle. 57                              ______________________________________                                         .sup.1) Cloud point was not observed at 5° C. or higher                .sup.2) Water solubility judgment criteria:                                   ⊚: very excellent                                              Δ: slightly opaque aqueous solution (dispersion)                        X: not dissolved                                                         

The novel amphipathic compound of the present invention prepared byadding EO to the allyl or vinyl compound having a succinamide structureor a succinic acid ester structure substituted with a hydrophobic groupin the skeleton shows good water solubility in a neutral or acid rangeas well as in an alkaline range. Accordingly, the compound of thepresent invention can be used as a reactive surfactant. In addition, thepolymerization conditions are not restricted when the compound of thepresent invention is copolymerized with various copolymerizableethylenically unsaturated compounds, and therefore it can be applied tovarious fields.

Amphipathic High Molecular Compound (I)

B-C₁₆ -ESA-MA/PAM Example 20

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of B-C₁₆ -ESA-MA obtained in Example 1 of 30.0 g,distilled water of 30.0 g and sodium hypophosphite of 0.15 g, and heatedto 80° C. while stirring under nitrogen flow. A mixed solution (cooledby an ice bath) of a 40% acrylamide aqueous solution of 67.5 g,distilled water of 172.1 g, and ammonium persulfate (hereinafterreferred to as APS) of 0.30 g was added dropwise to this solution with amicrotube pump in 120 minutes. Further, stirring was continued at 80° C.for 180 minutes to obtain a homogeneous pale yellow aqueous solution.The aqueous solution thus obtained had a viscosity of 63.5 cp and aweight-average molecular weight of 221,000.

Example 21

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen-introducing tube and a feed tube was charged with a 10%aqueous solution of B-C₁₆ -ESA-MA obtained in Example 1 of 60.0 g andsodium hypophosphite of 0.225 g, and heated to 80° C. while stirringunder nitrogen flow. A mixed solution (cooled by an ice bath) of a 40%acrylamide aqueous solution of 60.0 g, distilled water of 179.5 g, andAPS of 0.30 g was added dropwise to this solution with the microtubepump in 120 minutes. Further, stirring was continued at 80° C. for 180minutes to obtain a homogeneous pale yellow aqueous solution. Theaqueous solution thus obtained had a viscosity of 107.0 cp and aweight-average molecular weight of 125,000.

B-C₁₆ -ESA-DA/PAM Example 22

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10 taqueous solution of B-C₁₆ -ESA-DA obtained in Example 2 of 30.0 g,distilled water of 30.0 g and sodium hypophosphite of 0.225 g, andheated to 80° C. while stirring under nitrogen flow. A mixed solution(cooled by an ice bath) of a 40% acrylamide aqueous solution of 67.5 g,distilled water of 172.0 g, and APS of 0.30 g was added dropwise to thissolution with the microtube pump in 120 minutes. Further, stirring wascontinued at 80° C. for 180 minutes to obtain a homogeneous pale yellowaqueous solution. The aqueous solution thus obtained had a viscosity of15.3 cp and a weight-average molecular weight of 152,000.

Example 23

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10 %aqueous solution of B-C₁₆ -ESA-DA obtained in Example 2 of 60.0 g andsodium hypophosphite of 0.30 g, and heated to 80° C. while stirringunder nitrogen flow. A mixed solution (cooled on an ice bath) of a 40%acrylamide aqueous solution of 60.0 g, distilled water of 179.4 g, andAPS of 0.30 g was added dropwise to this solution with the microtubepump in 120 minutes. Further, stirring was continued at 80° C. for 180minutes to obtain a homogeneous pale yellow aqueous solution. Theaqueous solution thus obtained had a viscosity of 56.9 cp and aweight-average molecular weight of 174,000.

L-C₁₂ -PSA-MA/PAM Example 24

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₁₂ -PSA-MA obtained in Example 10 of 60.0 g andsodium hypophosphite of 0.60 g, and heated to 80° C. while stirringunder nitrogen flow. A mixed solution (cooled by an ice bath) of a 40%acrylamide aqueous solution of 135.0 g, distilled water of 103.8 g, andAPS of 0.60 g was added dropwise to this solution with the microtubepump in 120 minutes. Further, stirring was continued at 80° C. for 180minutes to obtain a homogeneous pale yellow aqueous solution. Theaqueous solution thus obtained had a non-volatile content of 21.6%, a pHof 6.96, a viscosity of 697 cp and a weight-average molecular weight of47,000.

Example 25

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₁₂ -PSA-MA obtained in Example 10 of 120.0 g andsodium hypophosphite of 0.90 g, and heated to 80° C. while stirringunder nitrogen flow. A mixed solution (cooled by an ice bath) of a 40%acrylamide aqueous solution of 120.0 g, distilled water of 58.2 g, andAPS of 0.90 g was added dropwise to this solution with the microtubepump in 120 minutes. Further, stirring was continued at 80° C. for 180minutes to obtain a homogeneous aqueous solution which was colored tothin yellow. The aqueous solution thus obtained had a non-volatilecontent of 21.4%, a pH of 7.30, a viscosity of 853 cp and aweight-average molecular weight of 9,100.

Example 26

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₁₂ -PSA-MA obtained in Example 10 of 180.0 g andsodium hypophosphite of 1.20 g, and heated to 80° C. while stirringunder nitrogen flow. A mixed solution (cooled by an ice bath) of a 40%acrylamide aqueous solution of 105.0 g, distilled water of 12.6 g, andAPS of 1.20 g was added dropwise to this solution with the microtubepump in 120 minutes. Further, stirring was continued at 80° C. for 180minutes to obtain a homogeneous pale yellow aqueous solution. Theaqueous solution thus obtained had a non-volatile content of 21.4%, a pHof 7.38, a viscosity of 571 cp and a weight-average molecular weight of5,000.

L-C₁₂ -PSA-DA/PAM Example 27

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₁₂ -PSA-DA obtained in Example 11 of 30.0 g,distilled water of 89.7 g and sodium hypophosphite of 0.30 g, and heatedto 80° C. while stirring under nitrogen flow. A mixed solution (cooledby an ice bath) of a 50% acrylamide aqueous solution of 54.0 g,distilled water of 125.7 g, and APS of 0.30 g was added dropwise to thissolution with the microtube pump in 120 minutes. Further, stirring wascontinued at 80° C. for 180 minutes to obtain a homogeneous pale yellowaqueous solution. The aqueous solution thus obtained had a non-volatilecontent of 10.8%, a pH of 6.43, a viscosity of 11.1 cp and aweight-average molecular weight of 25,000.

Example 28

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₁₂ -PSA-DA obtained in Example 11 of 60.0 g,distilled water of 59.4 g and sodium hypophosphite of 0.60 g, and heatedto 80° C. while stirring under nitrogen flow. A mixed solution (cooledby an ice bath) of a 50% acrylamide aqueous solution of 54.0 g,distilled water of 125.7 g, and APS of 0.30 g was added dropwise to thissolution with the microtube pump in 120 minutes. Further, stirring wascontinued at 80° C. for 180 minutes to obtain a homogeneous pale yellowaqueous solution. The aqueous solution thus obtained had a non-volatilecontent of 11.9%, a pH of 7.01, a viscosity of 6.9 cp and aweight-average molecular weight of 13,800.

Example 29

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10 %aqueous solution of L-C₁₂ -PSA-DA obtained in Example 11 of 90.0 g,distilled water of 29.1 g and sodium hypophosphite of 0.90 g, and heatedto 80° C. while stirring under nitrogen flow. A mixed solution (cooledby an ice bath) of a 50% acrylamide aqueous solution of 54.0 g,distilled water of 125.7 g, and APS of 0.30 g was added dropwise to thissolution with the microtube pump in 120 minutes. Further, stirring wascontinued at 80° C. for 180 minutes to obtain a homogeneous pale yellowaqueous solution. The aqueous solution thus obtained had a non-volatilecontent of 13.0%, a pH of 7.28, a viscosity of 6.3 cp and aweight-average molecular weight of 9,400.

L-C₂₄ -BSA-MA/PAM Example 30

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₂₄ -BSA-MA obtained in Example 12 of 30.0 g,distilled water of 29.7 g and sodium hypophosphite of 0.30 g, and heatedto 80° C. while stirring under nitrogen flow. A mixed solution (cooledby an ice bath) of a 50% acrylamide aqueous solution of 54.0 g,distilled water of 185.7 g, and APS of 0.30 g was added dropwise to thissolution with the microtube pump in 120 minutes. Further, stirring wascontinued at 80° C. for 180 minutes to obtain a homogeneous pale yellowaqueous solution. The aqueous solution thus obtained had a non-volatilecontent of 10.5%, a pH of 7.19, a viscosity of 8.4 cp and aweight-average molecular weight of 30,300.

Example 31

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10 %aqueous solution of L-C₂₄ -BSA-MA obtained in Example 12 of 60.0 g andsodium hypophosphite of 0.60 g, and heated to 80° C. while stirringunder nitrogen flow. A mixed solution (cooled by an ice bath) of a 50%acrylamide aqueous solution of 48.0 g, distilled water of 191.1 g, andAPS of 0.30 g was added dropwise to this solution with the microtubepump in 120 minutes. Further, stirring was continued at 80° C. for 180minutes to obtain a homogeneous pale yellow aqueous solution. Theaqueous solution thus obtained had a non-volatile content of 10.7% a pHof 7.72, a viscosity of 5.3 cp and a weight-average molecular weight of35,000.

Example 32

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₂₄ -BSA-MA obtained in Example 12 of 90.0 g andsodium hypophosphite of 0.90 g, and heated to 80° C. while stirringunder nitrogen flow. A mixed solution (cooled by an ice bath) of a 50%acrylamide aqueous solution of 42.0 g, distilled water of 166.8 g, andAPS of 0.30 g was added dropwise to this solution with the microtubepump in 120 minutes. Further, stirring was continued at 80° C. for 180minutes to obtain a homogeneous pale yellow aqueous solution. Theaqueous solution thus obtained had a non-volatile content of 10.8%, a pHof 7.91, a viscosity of 3.7 cp and a weight-average molecular weight of30,400.

L-C₂₄ -BSA-DA/PAM Example 33

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₂₄ -BSA-DA obtained in Example 13 of 30.0 g,distilled water of 29.7 g, and sodium hypophosphite of 0.30 g, andheated to 80° C. while stirring under nitrogen flow. A mixed solution(cooled by an ice bath) of a 50% acrylamide aqueous solution of 54.0 g,distilled water of 185.7 g, and APS of 0.30 g was added dropwise to thissolution with the microtube pump in 120 minutes. Further, stirring wascontinued at 80° C. for 180 minutes to obtain a homogeneous pale yellowaqueous solution. The aqueous solution thus obtained had a non-volatilecontent of 10.7%, a pH of 7.06, a viscosity of 7.28 cp and aweight-average molecular weight of 29,000.

Example 34

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₂₄ -BSA-DA obtained in Example 13 of 60.0 g andsodium hypophosphite of 0.60 g, and heated to 80° C. while stirringunder nitrogen flow. A mixed solution (cooled by an ice bath) of a 50%acrylamide aqueous solution of 48.0 g, distilled water of 191.1 g, andAPS of 0.30 g was added dropwise to this solution with the microtubepump in 120 minutes. Further, stirring was continued at 80° C. for 180minutes to obtain a homogeneous pale yellow aqueous solution. Theaqueous solution thus obtained had a non-volatile content of 10.6%, a pHof 7.50, a viscosity of 5.0 cp and a weight-average molecular weight of49,600.

Example 35

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₂₄ -BSA-DA obtained in Example 13 of 90.0 g andsodium hypophosphite of 0.90 g, and heated to 80° C. while stirringunder nitrogen flow. A mixed solution (cooled by an ice bath) of a 50%acrylamide aqueous solution of 42.0 g, distilled water of 166.8 g andAPS of 0.30 g was added dropwise to this solution with the microtubepump in 120 minutes. Further, stirring was continued at 80° C. for 180minutes to obtain a homogeneous pale yellow aqueous solution. Theaqueous solution thus obtained had a non-volatile content of 10.8%, a pHof 7.76, a viscosity of 4.4 cp and a weight-average molecular weight of29,500.

B-C₁₆ -ESA-AL/PAM Example 36

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of B-C₁₆ -ESA-AL obtained in Reference Example 1 of30.0 g, distilled water of 29.9 g and sodium hypophosphite of 0.15 g,and heated to 80° C. while stirring under nitrogen flow. A mixedsolution (cooled by an ice bath) of a 50% acrylamide aqueous solution of54.0 g, distilled water of 185.7 g and APS of 0.30 g was added dropwiseto this solution with the microtube pump in 120 minutes. Further,stirring was continued at 80° C. for 180 minutes to obtain a homogeneouspale yellow aqueous solution. The aqueous solution thus obtained had aviscosity of 478 cp and a weight-average molecular weight of 215,700.

Example 37

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen-introducing tube and a feed tube was charged with a 10%aqueous solution of B-C₁₆ -ESA-AL obtained in Reference Example 1 of60.0 g and sodium hypophosphite of 0.225 g, and heated to 80° C. whilestirring under nitrogen flow. A mixed solution (cooled by an ice icebath) of a 50% acrylamide aqueous solution of 48.0 g, distilled water of191.5 g and APS of 0.30 g was added dropwise to this solution with themicrotube pump in 120 minutes. Further, stirring was continued at 80° C.for 180 minutes to obtain a homogeneous pale yellow aqueous solution.The aqueous solution thus obtained had a viscosity of 8,190 cp and aweight-average molecular weight of 152,100.

Example 38

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of B-C₁₆ -ESA-AL obtained in Reference Example 1 of90.0 g and sodium hypophosphite of 0.45 g, and heated to 80° C. whilestirring under nitrogen flow. A mixed solution (cooled by an ice icebath) of a 50% acrylamide aqueous solution of 42.0 g, distilled water of167.3 g and APS of 0.30 g was added dropwise to this solution with themicrotube pump in 120 minutes. Further, stirring was continued at 80° C.for 180 minutes to obtain a homogeneous pale yellow aqueous solution.The aqueous solution thus obtained had a viscosity of 16.2 cp and aweight-average molecular weight of 30,400.

L-C₁₂ -PSA-AL/PAM Example 39

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₁₂ -PSA-AL obtained in Reference Example 3 of30.0 g, distilled water of 29.9 g and sodium hypophosphite of 0.15 g,and heated to 80° C. while stirring under nitrogen flow. A mixedsolution (cooled by an ice ice bath) of a 50% acrylamide aqueoussolution of 54.0 g, distilled water of 185.7 g and APS of 0.30 g wasadded dropwise to this solution with the microtube pump in 120 minutes.Further, stirring was continued at 80° C. for 180 minutes to obtain ahomogeneous pale yellow aqueous solution. The aqueous solution thusobtained had a non-volatile content of 10.6%, a pH of 7.10, a viscosityof 166 cp and a weight-average molecular weight of 32,000.

Example 40

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₁₂ -PSA-AL obtained in Reference Example 3 of60.0 g and sodium hypophosphite of 0.30 g, and heated to 80° C. whilestirring under nitrogen flow. A mixed solution (cooled by an ice icebath) of a 50° C. acrylamide aqueous solution of 48.0 g, distilled waterof 191.4 g and APS of 0.30 g was added dropwise to this solution withthe microtube pump in 120 minutes. Further, stirring was continued at80° C. for 180 minutes to obtain a homogeneous pale yellow aqueoussolution. The aqueous solution thus obtained had a non-volatile contentof 10.7%, a pH of 7.42, a viscosity of 51.0 cp and a weight-averagemolecular weight of 12,300.

Example 41

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₁₂ -PSA-AL obtained in Reference Example 3 of90.0 g and sodium hypophosphite of 0.38 g, and heated to 80° C. whilestirring under nitrogen flow. A mixed solution (cooled by an ice icebath) of a 50% acrylamide aqueous solution of 42.0 g, distilled water of167.3 g and APS of 0.30 g was added dropwise to this solution with themicrotube pump in 120 minutes. Further, stirring was continued at 80° C.for 180 minutes to obtain a homogeneous pale yellow aqueous solution.The aqueous solution thus obtained had a non-volatile content of 10.8%,a pH of 7.49, a viscosity of 60.2 cp and a weight-average molecularweight of 7,700.

L-C₂₄ -BSA-AL/PAM Example 42

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₂₄ -BSA-AL obtained in Reference Example 4 of30.0 g, distilled water of 29.9 g and sodium hypophosphite of 0.15 g,and heated to 80° C. while stirring under nitrogen flow. A mixedsolution (cooled by an ice ice bath) of a 50% acrylamide aqueoussolution of 54.0 g, distilled water of 185.7 g and APS of 0.30 g wasadded dropwise to this solution with the microtube pump in 120 minutes.Further, stirring was continued at 80° C. for 180 minutes to obtain anaqueous solution which was colored to pale yellow and slightly turbid.The aqueous solution thus obtained had a non-volatile content of 10.7%,a pH of 6.90, a viscosity of 17.3 cp and a weight-average molecularweight of 152,700.

Example 43

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₂₄ -BSA-AL obtained in Reference Example 4 of60.0 g and sodium hypophosphite of 0.30 g, and heated to 80° C. whilestirring under nitrogen flow. A mixed solution (cooled by an ice icebath) of a 50% acrylamide aqueous solution of 48.0 g, distilled water of191.4 g and APS of 0.30 g was added dropwise to this solution with themicrotube pump in 120 minutes. Further, stirring was continued at 80° C.for 180 minutes to obtain an aqueous solution which was colored to paleyellow and slightly turbid. The aqueous solution thus obtained had anon-volatile content of 10.7%, a pH of 7.32, a viscosity of 7.7 cp and aweight-average molecular weight of 163,500.

Example 44

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of L-C₂₄ -BSA-AL obtained in Reference Example 4 of90.0 g and sodium hypophosphite of 0.38 g, and heated to 80° C. whilestirring under nitrogen flow. A mixed solution (cooled by an ice icebath) of a 50% acrylamide aqueous solution of 42.0 g, distilled water of167.3 g and APS of 0.30 g was added dropwise to this solution with themicrotube pump in 120 minutes. Further, stirring was continued at 80° C.for 180 minutes to obtain a homogeneous aqueous solution which wascolored to pale yellow and slightly turbid. The aqueous solution thusobtained had a non-volatile content of 10.8%, a pH of 7.58, a viscosityof 7.1 cp and a weight-average molecular weight of 34,900.

B-C₁₆ -ESA-HM/PAM Example 45

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of B-C₁₆ -ESA-HM obtained in Example 14 of 15.0 g, a50% acrylamide aqueous solution of 57.0 g, distilled water of 221.4 g,sodium hydrogensulfite of 0.30 g and sodium hypophosphite of 0.30 g, andheated to 30° C. while stirring under nitrogen flow. A 10% APS aqueoussolution of 6.0 g was added to this solution. After continuing stirringat 30° C. for 180 minutes, a 10% APS aqueous solution and a 10% sodiumhydrogensulfite aqueous solution of each 0.9 g were added, and stirringwas further continued for 120 minutes to obtain an aqueous solutionwhich was slightly opaque. The aqueous solution thus obtained had anon-volatile content of 10.8%, a pH of 8.43, a viscosity of 176.2 cp anda weight-average molecular weight of 418,600.

Example 46

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of B-C₁₆ -ESA-HM obtained in Example 14 of 30.0 g, a50% acrylamide aqueous solution of 54.0 g, distilled water of 209.1 g,sodium hydrogensulfite of 0.30 g and sodium hypophosphite of 0.60 g, andheated to 30° C. while stirring under nitrogen flow. A 10% APS aqueoussolution of 6.0 g was added to this solution. After continuing stirringat 30° C. for 180 minutes, a 10% APS aqueous solution and a 10% sodiumhydrogensulfite aqueous solution of each 0.9 g were added, and stirringwas further continued for 120 minutes to obtain an aqueous solutionwhich was slightly opaque. The aqueous solution thus obtained had anon-volatile content of 10.9%, a pH of 8.64, a viscosity of 448.0 cp anda weight-average molecular weight of 186,100.

Example 47

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with a 10%aqueous solution of B-C₁₆ -ESA-HM obtained in Example 14 of 45.0 g, a50% acrylamide aqueous solution of 51.0 g, distilled water of 196.2 g,sodium hydrogensulfite of 0.30 g and sodium hypophosphite of 1.50 g, andheated to 30° C. while stirring under nitrogen flow. A 10% APS aqueoussolution of 6.0 g was added to this solution. After continuing stirringat 30° C. for 180 minutes, a 10% APS aqueous solution and a 10% sodiumhydrogensulfite aqueous solution of each 0.9 g was added, and stirringwas further continued for 120 minutes to obtain an aqueous solutionwhich were slightly opaque. The aqueous solution thus obtained had anon-volatile content of 11.1%, a pH of 8.78, a viscosity of 65.9 cp anda weight-average molecular weight of 85,400.

Comparative Example 1

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with distilledwater of 60.0 g and sodium hypophosphite of 0.05 g, and heated to 80° C.while stirring under nitrogen flow. A mixed solution (cooled by an iceice bath) of a 40% acrylamide aqueous solution of 150.0 g, distilledwater of 89.7 g and APS of 0.30 g was added dropwise to this solutionwith the microtube pump in 120 minutes. Further, stirring was continuedat 80° C. for 180 minutes to obtain a transparent, homogeneous aqueoussolution. The aqueous solution thus obtained had a viscosity of 2,680 cpand a weight-average molecular weight of 189,000.

All the following coating examples and coating comparative examples werecarried out using a base paper (basis weight 50 g/m²) for newspaper. Asizing degree was determined according to a Stockigt sizing test methodof JIS P8122; a surface strength was determined by measuring an RI pickwith model RI-3 (Akira Mfg. Co., Ltd.) (relative evaluation by a tenpoint system; the higher the point, the higher the surface strength);and a Z axis strength was determined with an internal bond tester(Kumagaya Riki Ind. Co., Ltd.).

Coating Examples 1 to 16

Base papers for coating were immersed in the polymer solutions obtainedin Examples 20 to 35 for one second and squeezed between two rolls.Then, the amounts of the solution absorbed were weighed to determine thecoated amounts. The concentrations of the coating solutions wereadjusted in advance so that the coated amounts in terms of non-volatilematters of the polymer were 1.0 g/m² in the case of Coating Examples 1to 4, 0.8 g/m² in the case of Coating Examples 5 to 10 and 1.2 g/m² inthe case of Coating Examples 11 to 16. The pH values of the coatingsolutions were adjusted to 7.8 to 8.2. Immediately after coating, thecoated paper was dried for 50 seconds in a drum drier in which thesurface temperature was set at 120° C., and after subjecting the driedpaper to humidity conditioning for 24 hours in a constant temperatureand humidity chamber (20° C., humidity 65%), the sizing degrees and thepaper strength were determined. The results thereof are shown in Table2.

Coating Examples 17 to 19

The polymer solutions obtained in Examples 45 to 47 were used to carryout the coating test in the same manner as in Coating Examples 1 to 16.The concentrations of the coating solutions were adjusted in advance sothat the coated amount in terms of non-volatile matters of the polymerwas 1.0 g/m². The results thereof are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Coating Test Result                                                           Coating      Polymerization                                                                       Coated                                                                              Coating                                                                             Steckigt sizing                                                                      RI Z axis                                Example rate wt % amount g/m.sup.2 solution pH degree (sec.) pick                                                     strength kg-cm                      __________________________________________________________________________    Blank        --     --    6.90  1.0    4.5                                                                              1.09                                   1 (Inv.) B-C.sub.16 -ESA-MA 10 1.0 7.81 32.6 9.0 1.78                         2 (Inv.) B-C.sub.16 -ESA-MA 20 1.0 8.21 37.2 8.0 1.62                         3 (Inv.) B-C.sub.16 -ESA-DA 10 1.0 7.85 33.5 8.5 1.71                         4 (Inv.) B-C.sub.16 -ESA-DA 20 1.0 8.10 34.1 8.0 1.63                         5 (Inv.) L-C.sub.12 -PSA-MA 10 0.8 8.02 24.7 8.5 1.74                         6 (Inv.) L-C.sub.12 -PSA-MA 18 0.8 8.15 27.6 8.5 1.70                         7 (Inv.) L-C.sub.12 -PSA-MA 25 0.8 8.16 28.2 8.0 1.64                         8 (Inv.) L-C.sub.12 -PSA-DA 10 0.8 7.87 25.1 8.5 1.72                         9 (Inv.) L-C.sub.12 -PSA-DA 18 0.8 7.95 27.0 8.0 1.71                        10 (Inv.) L-C.sub.12 -PSA-DA 25 0.8 8.04 25.5 8.0 1.63                        11 (Inv.) L-C.sub.24 -BSA-MA 10 1.2 7.35 29.6 9.0 1.85                        12 (Inv.) L-C.sub.24 -BSA-MA 20 1.2 7.42 34.2 8.5 1.78                        13 (Inv.) L-C.sub.24 -BSA-MA 30 1.2 7.48 32.5 8.0 1.74                        14 (Inv.) L-C.sub.24 -BSA-DA 10 1.2 7.36 27.1 8.5 1.82                        15 (Inv.) L-C.sub.24 -BSA-DA 20 1.2 7.45 29.8 8.5 1.77                        16 (Inv.) L-C.sub.24 -BSA-DA 30 1.2 7.45 28.9 8.0 1.75                        17 (Inv.) B-C.sub.16 -ESA-HM  5 1.0 7.63 25.5 8.5 1.83                        18 (Inv.) B-C.sub.16 -ESA-HM 10 1.0 7.92 26.8 8.5 1.79                        19 (Inv.) B-C.sub.16 -ESA-HM 15 1.0 7.95 26.7 8.0 1.76                        1 (Comp.) -- -- 0.8 6.85 1.5 8.0 1.63                                          -- -- 1.0 6.85 1.5 8.0 1.63                                                   -- -- 1.2 7.35 1.2 8.0 1.73                                                __________________________________________________________________________     RI pick conditions: Toyo Ink, ink tack 25, ink amount 0.4 ml, 60 rpm     

Coating Examples 20 to 34

Coated papers were prepared in the same manner as in Coating Examples 1to 16 to determine the sizing degrees and the paper strength, exceptthat the pH in coating was changed to 3.0 to 5.0. There were used thepolymer solutions obtained in Examples 20 to 23 for Coating Examples 20to 23 and those obtained in Examples 36 to 44 for Coating Examples 24 to32. The concentrations of the coating solutions were adjusted in advanceso that the coated amount in terms of non-volatile matters of thepolymer was 1.0 g/m². The results thereof are shown in Table 3. On thepH condition of the present coating examples, ASA-MA, ASA-AL and ASA-HMdecreased in solubility in water to turn into emulsions, but thepolymers prepared by copolymerizing with acrylamide were transparentviscous aqueous solutions.

                                      TABLE 3                                     __________________________________________________________________________    Coating Test Result                                                           Coating      Polymerization                                                                       Coated                                                                              Coating                                                                             Steckigt sizing                                                                      RI Z axis                                Example rate wt % amount g/m.sup.2 solution pH degree (sec.) pick                                                     strength kg-cm                      __________________________________________________________________________    Blank        --     --    4.88  1.0    4.5                                                                              1.02                                  20 (Inv.) B-C.sub.16 -ESA-MA 10 1.0 3.02 30.6 8.5 1.74                        21 (Inv.) B-C.sub.16 -ESA-MA 20 1.0 4.01 32.5 8.0 1.71                        22 (Inv.) B-C.sub.16 -ESA-DA 10 1.0 3.93 30.7 8.5 1.70                        23 (Inv.) B-C.sub.16 -ESA-DA 20 1.0 3.80 32.8 8.5 1.64                        24 (Inv.) B-C.sub.16 -ESA-AL 10 1.0 4.52 29.8 8.5 1.79                        25 (Inv.) B-C.sub.16 -ESA-AL 20 1.0 4.79 30.4 8.0 1.73                        26 (Inv.) B-C.sub.16 -ESA-AL 30 1.0 4.96 27.5 8.0 1.70                        27 (Inv.) L-C.sub.12 -PSA-AL 10 1.0 4.60 26.5 8.5 1.78                        28 (Inv.) L-C.sub.12 -PSA-AL 20 1.0 4.82 29.3 8.0 1.72                        29 (Inv.) L-C.sub.12 -PSA-AL 30 1.0 4.89 27.7 8.0 1.66                        30 (Inv.) L-C.sub.24 -BSA-AL 10 1.0 4.55 25.5 8.5 1.79                        31 (Inv.) L-C.sub.24 -BSA-AL 20 1.0 4.78 31.8 8.0 1.68                        32 (Inv.) L-C.sub.24 -BSA-AL 30 1.0 4.95 30.4 8.0 1.64                      __________________________________________________________________________     RI pick conditions: Toyo Ink, ink tack 25, ink amount 0.4 ml, 60 rpm     

Coating Comparative Example 1

A coated paper was prepared in the same manner as in Coating Examples 1to 16 to determine a sizing degree and a paper strength, except that thepolymer was changed to one produced in Comparative Example 1. Theresults thereof are shown in Table 2.

As apparent from the examples, the amphipathic compound of the presentinvention used as a copolymerizable component for acrylamide polymersprovides compounds which are useful as paper making additives having notonly an excellent paper reinforcing performance but also a good sizingperformance. The actions thereof are not necessarily clarified, but itis considered that an amide group of the copolymer forms a hydrogen bondwith cellulose fiber in a drying step after coating and this improvesthe paper strength to a large extent and that the alkenyl groups arecoagulated to be oriented on the surface of the paper, whereby thesizing performance is exhibited.

Amphipathic High Molecular Compound (III)

The amphipathic compound (III) of the present invention shall beexplained in detail but the present invention shall not be restricted tothese examples. In the following examples, percentage is based onweight, and viscosity is a value determined with a B type viscometer at25° C.

Example 48

A 20 wt % aqueous solution of B-C₁₆ -ESA-MA obtained in Example 1 of50.0 g, sodium hypophosphite monohydrate of 0.25 g and distilled waterof 469.8 g were blended homogeneously in a flask, and then the pH wasadjusted to 9.0. After substituting the air in the flask with nitrogen,the mixed solution contained in the flask was heated to 80° C., and thenan aqueous solution prepared by blending homogeneously a 50% acrylamideaqueous solution of 161.2 g, DM of 9.4 g, 35% hydrochloric acid of 6.2g, distilled water of 302.7 g and APS of 0.5 g, and then adjusting thepH to 4.5 with a 10% sodium hydroxide aqueous solution was added throughthe feed tube with the microtube pump in 120 minutes. One hour afterfinishing the addition, a 2.5% APS aqueous solution of 10 ml and a 2.5%sodium sulfite (SBS) aqueous solution of 10 ml were added, and stirringwas further continued at 80° C. for 2 hours, whereby a bluish whiteaqueous solution was obtained. The aqueous solution thus obtained had asolid concentration of 10.7%, a viscosity of 20.1 cp and a pH of 6.70.

Examples 49 to 52

The polymerization was carried out in the same manner as in Example 48,except that the compositions were changed as shown in Table 4. Theresults thereof are shown in Table 4.

Examples 53 to 55

The polymerization was carried out in the same manner as in Examples48-50 to obtain a transparent viscous liquid, except that the amounts ofsodium hypophosphite (chain transfer agent) and APS (polymerizationinitiator) are changed as shown in Table 4. The results are shown inTable 4.

Example 56

A four neck flask of 1 l equipped with a stirrer, a reflux condenser, anitrogen introducing tube and a feed tube was charged with a 80 wt %aqueous solution of B-C₁₈ -ESA-MA produced in Example 3 of 25.0 g,sodium hypophosphite monohydrate of 0.75 g and distilled water of 494.3g to blend them homogeneously, and then the pH was adjusted to 9.0.After substituting the air in the flask with nitrogen, the mixedsolution contained in the flask was heated to 80° C., and then anaqueous solution prepared by blending homogeneously a 50% acrylamideaqueous solution of 160.0 g, 35% hydrochloric acid of 2.9 g, distilledwater of 316.6 g and APS of 0.50 g was added through the feed tube withthe microtube pump in 120 minutes. One hour after finishing theaddition, a 2.5% APS aqueous solution of 10 ml and a 2.5% SBS aqueoussolution of 10 ml were added, and stirring was further continued at 80°C. for 2 hours, whereby a slightly opaque aqueous solution was obtained.The aqueous solution thus obtained had a solid concentration of 10.3%, aviscosity of 19.0 cp, and a pH of 7.35.

Examples 57 to 61

The polymerization was carried out in the same manner as in Example 56,except that the compositions were changed as shown in Table 4. Theresults are shown in Table 4.

                                      TABLE 4                                     __________________________________________________________________________    Polymerization Results                                                                                      Polymerization Chain Transfer                                                                             Average             Copolymerization composition  initiator                                                                             agent   Concen-     molecular           Example                                                                            AAM ASA-MA.sup.1)                                                                         Colloidizing agent                                                                         Ammonium                                                                              Sodium hypo-                                                                          tration                                                                              Viscos-                                                                            weight              No.  wt %                                                                              Kind                                                                              wt %                                                                              Kind     mol %.sup.2)                                                                      persulfate wt %.sup.3)                                                                phosphite wt %.sup.3)                                                                 wt %                                                                              pH ity cp                                                                             MW                  __________________________________________________________________________    48   90  B-C.sub.16                                                                        10  DM hydrochloride                                                                       230 0.50    0.25    10.3                                                                              6.70                                                                             20.1 289,000                                                                        49 80 B-C.sub.1                                                              6 20 DM                                                                       hydrochloride                                                                 100  0.50 0.50                                                                10.4 7.42 67.4                                                                265,800                                                                        50 70 B-C.sub.1                                                              6 30 DM                                                                       hydrochloride                                                                 60 0.50 1.00                                                                  10.3 7.71 892                                                                 196,000                                                                        51 90 B-C.sub.1                                                              6 10 Itaconic                                                                 acid 48 0.50                                                                  0.50 10.9 6.43                                                                226 223,000                                                                    52 90 B-C.sub.1                                                              6 10 Hydrochlori                                                              c acid 48 0.50                                                                0.50 10.9 7.13                                                                28.2 307,000                                                                   53 90 B-C.sub.1                                                              6 -- -- -- 1.00                                                               1.00 10.6 7.62                                                                19.7  8,700                                                                    54 80 B-C.sub.1                                                              6 20 -- -- 1.50                                                               1.50 10.6 7.68                                                                14.1  4,900                                                                    55 70 B-C.sub.1                                                              6 30 -- -- 2.00                                                               2.00 10.5 7.92                                                                7.6  3,200                                                                     56 80 B-C.sub.1                                                              8 20 Hydrochlori                                                              c acid 53 0.50                                                                0.75 10.3 7.35                                                                19.0 357,000                                                                   57 70 B-C.sub.1                                                              8 30 Hydrochlori                                                              c acid 50 0.50                                                                1.00 10.3 7.56                                                                12.7 268,000                                                                   58 80 B-C.sub.1                                                              8 20 DM                                                                       hydrochloride                                                                 120  0.50 0.50                                                                10.2 7.62 40.0                                                                218,000                                                                        59 70 B-C.sub.1                                                              8 30 DM                                                                       hydrochloride                                                                 70 0.50 1.00                                                                  10.5 7.87 36.0                                                                172,000                                                                        60 80 B-C.sub.1                                                              8 20 Itaconic                                                                 acid 50 0.50                                                                  0.50 10.4 7.55                                                                66.9 451,000                                                                   61 70 B-C.sub.1                                                              8 30 Itaconic                                                                 acid 30 0.50                                                                  0.70 10.1 8.04                                                                55.6 241,000        __________________________________________________________________________     .sup.1) Concentration as sodium salts;                                        .sup.2) value based on ASAMA;                                                 .sup.3) value based on solid content of total monomers                   

Comparative Examples 2 to 7

The polymerization was carried out in the same manners and the samecompositions as in Examples 48 to 52, except that distilled water wassubstituted for DM and 35% hydrochloric acid, and the whole solution wassolidified in a gel form in the middle of the addition, which made itimpossible to continue the polymerization in a homogeneous system.Accordingly, the polymerization was stopped.

Comparative Examples 8 to 12

The polymerization was carried out in the same manners and the samecompositions as in Examples 56 to 61, except that distilled water wassubstituted for DM and 35% hydrochloric acid, and the whole solution wassolidified in a gel form in the middle of the addition, which made itimpossible to continue the polymerization in a homogeneous system.Accordingly, the polymerization was stopped.

Water Dispersible Resin Composition (IV)

The amphipathic compound (IV) of the present invention shall beexplained in detail but the present invention shall not be restricted tothese examples. In the following examples, percentage is based onweight, and viscosity is a value determined with a B type viscometer at25° C. In emulsion aqueous solutions, viscosity is a value determined byfixing the revolution to 30 rpm since the emulsion aqueous solutionsshow thixotropy.

Example 62

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with an aqueoussolution prepared by blending homogeneously a 20 wt % aqueous solutionof B-C₁₆ -ESA-MA produced in Example 1 of 15.0 g, distilled water of134.6 g, and sodium hypophosphite monohydrate of 0.075 g, and heated to80° C. while stirring after substituted the air in the flask withnitrogen. A solution prepared by blending homogeneously a 50% acrylamideaqueous solution of 48.4 g, DM of 2.8 g, distilled water of 66.9 g andAPS of 0.15 g and then adjusting the pH to 6.0 with 35% hydrochloricacid of 1.8 g was added to the above solution through the feed tube in 2hours. Stirring was continued for one hour after finishing the addition,whereby a slightly opaque aqueous solution was obtained. Subsequently, amixed solution of styrene of 30.0 g and benzoyl peroxide (BPO) of 0.3 gwas added dropwise to this aqueous solution through the feed tube in 20minutes, and stirring was further continued at 80° C. for 3 hours,whereby an opal emulsion solution was obtained. The emulsion aqueoussolution thus obtained had a solid concentration of 20.3%, a pH of 6.22and a viscosity of 96.0 cp.

Examples 63 to 64

The polymerization was carried out in the same manner as that in Example62, except that the monomer compositions were changed as shown in Table5. Provided that styrene was added dropwise in 30 minutes in Example 63and in 40 minutes in Example 64 to obtain opal emulsions in both cases.The results thereof are summarized in Table 5.

Examples 65 to 67

The polymerization was carried out in the same manner as in Examples 62to 64, except that the hydrophobic monomer was changed from styrene tomethyl methacrylate (MMA), whereby opal emulsions were obtained.

Example 68

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen introducing tube and a feed tube was charged with an aqueoussolution prepared by blending homogeneously a 20 wt % aqueous solutionof B-C₁₆ -ESA-MA produced in Example 1 of 50.0 g, distilled water of469.8 g, and sodium hypophosphite monohydrate of 0.25 g, and heated to80° C. while stirring after substituted the air in the flask withnitrogen. A solution prepared by blending homogeneously a 50% acrylamideaqueous solution of 161.2 g, DM of 9.4 g, distilled water of 303.0 g,and APS of 0.50 g and then adjusting the pH to 4.5 with 35% hydrochloricacid of 5.9 g was added to the above solution through the feed tube in 2hours. One hour after finishing the addition, a 2.5% APS aqueoussolution of 10 ml and a 2.5% SBS aqueous solution of 10 ml were added,and stirring was further continued at 80° C. for 2 hours, whereby aslightly opaque aqueous solution was obtained. This solution had a solidconcentration of 10.5%, a pH of 6.86 and a viscosity of 24.5 cp. Thishigh molecular surfactant aqueous solution is designated as PD-1.

A four neck flask of 300 ml equipped with a stirrer, a reflux condenser,a nitrogen-introducing tube and a feed tube was charged with an aqueoussolution prepared by dissolving homogeneously PD-1 of 142.5 g, distilledwater of 7.35 g and potassium persulfate (KPS) of 0.15 g, and heated upto 60° C. while stirring after substituted the air in the flask withnitrogen. A mixed solution of MMA of 27.0 g and 2-ethylhexyl acrylate(2EHA) of 3.0 g was added dropwise through the feed tube in 60 minutes,and stirring was further continued at 60° C. for 7 hours, whereby anopal emulsion solution was obtained. The emulsion solution had a solidconcentration of 24.3%, a pH of 5.71 and a viscosity of 640 cp.

Examples 69 to 73

The polymerization was carried out in the same manner as in Example 68,except that the composition of the hydrophobic monomer was changed asshown in Table 5. The results thereof are summarized in Table 5.

                                      TABLE 5                                     __________________________________________________________________________    Emulsion Polymerization, Result                                                          Hydrophobic Polymerization                                                                       Emulsion polymerization result                  A:B.sup.1) monomer.sup.2)                                                                            initiator.sup.3)                                                                     Concen-     Particle                            Example                                                                            (composition                                                                        Styrene                                                                           MMA 2 EHA                                                                             BPO                                                                              KPS tration                                                                              Viscosity                                                                          diameter.sup.4)                       No. Ratio) wt % wt % wt % wt % wt % wt % pH cp nm                           __________________________________________________________________________    62   50:50 100 --  --  1  --  20.3                                                                              6.22                                                                             96.0 208                                   63 40:60 100 -- -- 1 -- 24.7 5.84 161 341                                     64 33:67 100 -- -- 1 -- 28.9 5.55 320 457                                     65 50:50 -- 100 -- 1 -- 19.6 6.25 68.0 216                                    66 40:60 -- 100 -- 1 -- 23.5 5.88 220 274                                     67 33:67 -- 100 -- 1 -- 28.5 6.17 256 330                                     68 33:67 --  90 10 -- 1 24.3 5.71 640 249                                     69 33:67 --  80 20 -- 1 25.6 5.65 519 266                                     70 33:67 --  70 30 -- 1 25.1 5.76 295 241                                     71 33:67  90 -- 10 -- 1 25.0 5.64 351 450                                     72 33:67  80 -- 20 -- 1 25.1 5.63 334 437                                     73 33:67  70 -- 30 -- 1 24.7 5.70 270 546                                     PD-1 -- -- -- -- -- -- 10.5 6.86 24.5 214                                   __________________________________________________________________________     .sup.1) High molecular surfactant (A): hydrophobic monomer (B) in terms o     a solid weight ratio.                                                         .sup.2) Composition ratio of the hydrophobic monomers.                        .sup.3) Addition amount (wt %) based on the total amounts of the              hydrophobic monomers.                                                         .sup.4) Value in the aqueous solution of pH 5.5.                         

Comparative Examples 13 to 18

The polymerization was carried out in the same manners as in Examples 62to 67 without using B-C₁₆ -ESA-MA. The solutions were coagulated duringthe polymerization of the hydrophobic monomers, and therefore emulsionscould not be obtained.

Particle Diameter Measuring Examples 1 to 6

The particle diameters of the emulsions obtained in Examples 62 to 67were determined in the aqueous solutions with a Coal Tar N4 typesubmicron particle analyzer manufactured by Coal Tar Co., Ltd. inscattered light of 90°. The results thereof are summarized in Table 5.Further, the particle diameter of the high molecular surfactant alonebefore adding the hydrophobic monomer was shown together.

Coagulations are formed during the emulsion-polymerization of thehydrophobic monomers in the presence of the polymers in which ASA-MA isnot copolymerized, and therefore the emulsifiers are essential forforming the emulsions. It is supposed, however, that since emulsionparticles have a weak interaction with water soluble polymers inprinciple, the most part of the polymers can not stay on particlesurfaces even with emulsifiers. According to the present invention,emulsions having excellent stability can be prepared in the presence ofthe high molecular surfactant of the present invention. Further, thehigh molecular surfactant has an ability to form colloid particles byitself, and the copolymerized amount of hydrophobic monomers exceeding afixed amount (about 10%) increases the particles in whole. Accordingly,it is judged that hydrophilic polymers free from the particles arescarcely present.

Water dispersible Resin Composition (II)

The water dispersible resin composition (II) of the present inventionshall be explained but the present invention shall not be restricted tothese examples. In the following examples, percentage is based onweight, and viscosity is a value determined with a B type viscometer at25° C.

Example 74

Styrene of 100.0 g was added dropwise to an aqueous solution prepared bydissolving homogeneously a 80 wt % aqueous solution of B-C₁₈ -ESA-MAproduced in Example 3 of 6.53 g in distilled water of 53.5 g in 30minutes while stirring vigorously with a magnetic stirrer to prepare anopal monomer emulsion. A four neck flask of 300 ml equipped with astirrer, a reflux condenser, a nitrogen introducing tube and a droppingfunnel was charged with distilled water of 98.3 g, and heated to 80° C.after substituting the air in the flask with nitrogen, followed byadding a 10% potassium persulfate aqueous solution of 5.0 g. Then, amonomer emulsion prepared in advance was continuously added dropwisefrom the dropping funnel in 2 hours. After finishing the addition,ripening was carried out for 2 hours to obtain an opal stable emulsionfree of coagulations. This emulsion had a pH of 8.20, a solidconcentration of 40.5% and a viscosity of 8.5 cp. The results thereofare summarized in Table 6.

Examples 75 to 77

The polymerization was carried out in the same manner as in Example 74,except that the monomer compositions were changed as shown in Table 6,and opal, good emulsions were obtained in all examples. The results aresummarized in Table 6.

Example 78

Styrene of 100.0 g was added dropwise to an aqueous solution prepared bydissolving homogeneously a 80 wt % aqueous solution of B-C₁₈ -ESA-MAproduced in Example 3 of 6.55 g in distilled water of 53.5 g in 30minutes while stirring vigorously with a magnetic stirrer to prepare anopal monomer emulsion. A four neck flask of 300 ml equipped with astirrer, a reflux condenser, a nitrogen introducing tube and a droppingfunnel was charged with distilled water of 98.3 g, and heated to 80° C.after substituting the air in the flask with nitrogen, followed byadding a 10% potassium persulfate aqueous solution of 5.0 g. Then, amonomer emulsion prepared in advance was continuously added dropwisefrom the dropping funnel in 2 hours. After finishing the addition,ripening was carried out for 2 hours to obtain an opal stable emulsionfree of coagulations. This emulsion had a pH of 8.35, a solidconcentration of 41.3% and a viscosity of 10.6 cp. The results thereofare summarized in Table 6.

Comparative Example 19

The polymerization was carried out in the same manner as in Example 74,except that sodium alkylbenzenesulfonate was substituted for ESA-MA, andthe same amount of distilled water was substituted for 40% sodiumhydroxide, whereby an opal emulsion was obtained. The results aresummarized in Table 6.

[Evaluation of Films]

The emulsion solutions obtained in Examples 74 to 78 and ComparativeExample 19 were dried at room temperatures by a cast method to preparefilms of 0.25 mm. After the dried films were immersed in a 1.0%hydrochloric acid aqueous solution for 30 minutes, water dropletsremaining on film surfaces were wiped off with filter papers, and thenthe films were subjected to heat treatment in a constant temperaturedrier of 100° C. for one hour. A waterproof test was carried out by amethod in which the films were immersed in distilled water at roomtemperatures to determine a water absorption amount. A water absorptionrate (%) was represented by a weight percentage (%) of the waterabsorption amount per polymer film. The same test was carried out aswell in Comparative Example 19, and the results are shown in Table 7.

                  TABLE 6                                                         ______________________________________                                        Emulsion Polymerization Results                                                                      Polymerization                                                      Monomer   result                                                              composition      Solid   Vis-                                    Example            St      MMA        content                                                                             cosity                              No. Emulsifier (wt%) (wt%) pH (wt%) (cp)                                    ______________________________________                                        74     B--C.sub.18 -ESA-MA                                                                       100     --    8.20 40.5   8.5                                (Inv.)                                                                        75 B--C.sub.18 -ESA-MA  70 30 8.25 40.3 11.3                                  (Inv.)                                                                        76 B--C.sub.18 -ESA-MA  60 40 8.22 40.5  7.3                                  (Inv.)                                                                        77 B--C.sub.18 -ESA-MA  50 50 8.35 40.6  7.0                                  (Inv.)                                                                        78 B--C.sub.18 -ESA-MA 100 -- 8.15 40.2  5.1                                  (Inv.)                                                                        19 ABS 100 -- 7.02 40.6 10.5                                                  (Comp.)                                                                     ______________________________________                                         St: styrene,                                                                  MMA: methyl methacrylate,                                                     ABS: sodium alkylbenzenesulfonate                                        

                  TABLE 7                                                         ______________________________________                                        Waterproof Test Results                                                                  Water absorption rate (%)                                          Example    Immersing time                                                     No.        1 hour  2 hours    4 hours                                                                             8 hours                                   ______________________________________                                        74 (Inv.)  0       0          1     1                                           75 (Inv.) 0 1 1 2                                                             76 (Inv.) 1 1 2 3                                                             77 (Inv.) 1 1 2 4                                                             78 (Inv.) 1 1 2 4                                                             19 (Comp.) 5 8 10   25                                                      ______________________________________                                    

Heat resistance was evaluated by determining a Tg (glass transitiontemperature) by a transition temperature measuring method with DSC(DSC-50: manufactured by Shimadzu Mfg. Co., Ltd.) according to JISK-7121-1987. A standard sample (standard pellet manufactured byScientific Polymer Products, INC.) of polystyrene had a Tg of 104° C.; afilm produced from the emulsion obtained in Example 74, which was notsubjected to acid treatment, had a Tg of 102° C., and the film samplewhich was subjected to heat treatment after the acid treatment had a Tgof 106° C.; and the film prepared in Comparative Example 19 had a Tg of100° C.

The water dispersible resin composition of the present invention is astable emulsion, and as apparent from the examples, a polymer filmobtained from the emulsion is excellent in water resistance and heatresistance as compared with films produced by using conventionalsurfactants as emulsifiers. The actions thereof are not necessarilyclarified, but the excellent water resistance and heat resistancedescribed above are considered to originate in the fact that since thesuccinic acid allylamide type reactive surfactant is highlycopolymerizable, free monomers are scarcely found after thepolymerization. Further, it is considered that in the polymer filmshaving a succinic acid monoallylamide structure, succinamide bringsabout cyclodehydration by subjecting the polymer films to acid and heattreatment to form an imide structure and therefore the variousperformances are further improved.

What is claimed is:
 1. A high molecular compound obtained by copolymerizing 0.1 to 90.0 weight % of an amphipathic compound having a succinic acid skeleton represented by any of the following Formulas (18) to (19) or a mixture thereof with 10.0 to 99.9 weight % of a copolymerizable ethylenically unsaturated compound: ##STR14## wherein R₁ is a linear or branched, saturated hydrocarbon group having 6 to 48 carbon atoms, or a linear or branched, unsaturated hydrocarbon group containing 1 to 12 unsaturated double bond and having 6 to 48 carbon atoms; R₂ is a hydrogen atom or a methyl group; M is hydrogen atom, alkali metal, or an ammonium group; and Y is NH or N--(CH₂ --CH═CH₂).
 2. A water soluble or dispersible amphipathic high molecular compound obtained by copolymerizing 0.1 to 90.0 weight % of the compound represented by any of the following Formulas (18) to (21) or a mixture thereof with 10.0 to 99.9 weight % of a hydrophilic ethylenically unsaturated compound: ##STR15## wherein R₁ is a linear or branched, saturated hydrocarbon group having 6 to 48 carbon atoms, or a linear or branched, unsaturated hydrocarbon group containing 1 to 12 unsaturated doble bonds and having 6 to 48 carbon atoms; R₂ and R₃ are independently a hydrogen atom or a methyl group; R₄ is a linear or branched, saturated hydrocarbon group having 2 to 6 carbon atoms; M is a hydrogen atom, alkali metal, or an ammonium group; and Y is NH, N--(CH₂ --CH═CH₂), or O.
 3. A paper making additive containing the water soluble or dispersible amphipathic high molecular compound as described in claim 2 as an active ingredient.
 4. A process for producing an amphipathic high molecular compound comprising copolymerizing a reactive surfactant with a hydrophilic, nonionic unsaturated compound in an aqueous medium in the presence of a colloidizing agent wherein the reactive surfactant is represented by any of Formulas (18) to (19): ##STR16## wherein R₁ is a linear or branched, saturated hydrocarbon group having 6 to 48 carbon atoms, or a linear or branched, unsaturated hydrocarbon group containing 1 to 12 unsaturated double bonds and having 6 to 48 carbon atoms; R₂ is a hydrogen atom or a methyl group; M is a hydrogen atom, alkali metal, or an ammonium group; and Y is NH or N--(CH₂ --CH═CH₂).
 5. A process for producing an amphipathic high molecular compound as described in claim 4, wherein 0.1 to 90 weight % of the reactive surfactant is copolymerized with 10 to 99.9 weight % of the hydrophilic, nonionic ethylenically unsaturated compound in the aqueous medium in the presence of the colloidizing agent in an amount of 0.1 to 10 moles per mole of the reactive surfactant.
 6. A process for producing an amphipathic high molecular compound as described in claim 5, wherein the colloidizing agent comprises at least one or a combination selected from an inorganic acid, an organic acid, an inorganic base, and an organic base.
 7. A process for producing an amphipathic high molecular compound as described in claim 4, wherein the colloidizing agent comprises at least one or a combination selected from an inorganic acid, an organic acid, an inorganic base, and an organic base.
 8. A process for producing an amphipathic high molecular compound as described in claim 4, wherein the reactive surfactant has at least one carboxyl group in the molecule.
 9. A process for producing an amphipathic high molecular compound as described in claim 8, wherein 10 to 99.9 weight % of the hydrophilic, nonionic ethylenically unsaturated compound is copolymerized with 0.1 to 90 weight % of the reactive surfactant having at least one carboxyl group in the molecule in an aqueous medium in the presence of the colloidizing agent in an amount of 0.1 to 10 moles per mole of the reactive surfactant.
 10. A process for producing an amphipathic high molecular compound as described in claim 9, wherein the colloidizing agent comprises at least one or a combination selected from an inorganic acid, an organic acid, an inorganic base, and an organic base. 